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# Influence of auto-organization and fluctuation effects on the kinetics of a monomer-monomer catalytic scheme.

## I Introduction

Catalytically activated processes play a significant role in numerous technologies as they serve to produce required products from the species which are non-reactive in normal physical conditions; these chemically stable species may, however, enter into reaction in the presence of some third substance - the catalytic substrate . Despite of the widespread use of such processes, the knowledge of the underlying physics and chemistry still rests largely on phenomenological ideas and prescriptions, and thus remains a challenge for fundamental research .

At the simplest, mean-field level of description, reaction kinetics theory presumes that the reaction rate should be considered as the product of the reactant densities and the rate constant, which is dependent on the nature of the binding forces and on the particles’ dynamics. This rate constant is proportional to the hopping rate if the process is diffusion controlled, or to the reaction frequency, in case when the reaction is kinetically controlled . Hence, a clear cut separation is presumed to exist between the local variables, that could be derived, say, from quantum mechanics, and collective variables, expressed in the most simple way as the product of mean densities of the particles involved.

Recently, one of the most active developments in the field has been the recognition of the substantial importance of the multi-particle effects, spatial fluctuations and self-organization, as opposed to conventional local energetic considerations, which emphasized the purely chemical constraints and focused on the refined descriptions of the elementary reaction act. Subsequently, statistical physics concepts were introduced in order to describe anomalous fluctuation-induced behaviors of non-catalytic chemical reactions  and simplest catalytic schemes , as well as such to gain a better understanding of such collective phenomena as wave formation, presence of excitable media or stochastic aggregation in chemical systems (see Refs. and references therein). One conclusion that can be drawn from the statistical physics approach is that fluctuations, either spatial or temporal, may drive the reactive system into a set of new states, that cannot be understood and described in terms of mean-field kinetic equations.

In this paper we discuss in detail the influence of spatial fluctuations, statistical self-organization effects and effects of random diffusive motion of reactants on the kinetics of catalytic reactions, using as a particular example the Langmuir-Hinshelwood type reaction scheme. This reaction process, which is also often referred to as the monomer-monomer catalytic scheme, involves two different kinds of species, $`A`$ and $`B`$, which are deposited (continuously in time with mean intensity $`I`$) onto the catalytic substrate by an external source, diffuse on the substrate and react at encounters forming an inert reaction product $`O`$, $`A+BO`$, which is then removed from the system. Our aims here are twofold. First, we show that this seemingly simple catalytic reaction (which has, in fact, several practical applications (see, e.g. Ref.)) shows quite a rich behavior and represents an ideal illustrative example of the statistical physics effects in the reaction kinetics, which may be generic to more complicated schemes involved in real ”stuff” catalytic processes. Second, we develop a unified analytical description which takes into account explicitly the influence of spatial correlations, dimensionality of space and the way how the particles are introduced into the reaction bath on the time evolution of observables - mean particle densities. Moreover, our approach can be routinely generalized for kinetic description of more complex reaction schemes.

We focus here on several different aspects of the Langmuir-Hinshelwood reaction scheme. In particular, we address the question of how the kinetics depends on the dimensionality $`d`$ of the reactive system. In addition to the standard Langmuir-Hinshelwood model in which the catalytic substrate is a two dimensional flat surface, we analyse kinetics of $`A+B0`$ reactions followed by an external input of reactive species in one- and three-dimensional systems, i.e. the situations appropriate to reactions in capillary geometries  and annealing of the radiation damage in solids . We show that the monomer-monomer catalytic reaction proceeds quite differently in low dimensional ($`d=1,2`$) and three-dimensional systems. Besides, we examine how the way of particles’ injection into the system affects the properties of stationary states and also how these stationary states are approached in time. We consider here two different types of external input; in the first one (case I) the $`A`$ and $`B`$ particles are introduced independently of each other at random moments of time and at random positions in space, while in the second case (case II) an $`A`$ and a $`B`$ species are introduced in correlated pairs of a fixed radius, the pairs being injected at random moments of time and at random positions in space. We show that also the way of input does matter significantly and may result in a completely different behavior.

The paper is structured as follows: In Section II we formulate the model, introduce a general analytic approach and, in terms of this approach, derive closed-form equations describing the time evolution of mean particles’ densities and pairwise correlation functions. In Section III we present solution to these equations in one-, two- and three-dimensional systems corresponding to different ways of particles injection to the reaction bath. Finally, we conclude in Section IV with a brief summary of our results and discussion.

## II Definitions and basic equations.

In this section we present kinetic description of the monomer-monomer catalytic scheme involving diffusive particles in terms of a certain analytical approach, which takes explicitly into account the influence of pairwise correlations on the time evolution of mean densities; such a description has been first proposed in Ref., which analysed the effects of fluctuations on the kinetics of $`A+BO`$ reactions and yielded the celebrated $`t^{d/4}`$-law for the decrease of particles mean densities. The subsequent works  extended this approach to more general reaction schemes (e.g. reversible and coagulation reactions), three-body and catalytic reactions, and also included the possibility of mutual long-ranged interparticle interactions. Here we will focus on the application of this approach to the analytical description of the $`A+BO`$ reactions kinetics in systems with a continuous, random external input of the reactive species. We will recover some of already known results obtained for the monomer-monomer catalytic scheme involving diffusive monomers and will establish several new ones concerning the long-time relaxation of mean particles density to their steady-state values and the dependence of this steady-state densities on the system parameters.

We start with the formulation of the model. Consider a $`d`$-dimensional reaction bath of volume $`V`$ (we suppose that $`V`$ is sufficiently large such that we can discard different finite-size effects, e.g. hard-core exclusion between particles, the termination of reaction within a finite time interval or saturation (poisoning)) in which $`A`$ and $`B`$ particles are continiously introduced by an external random source. The statistical properties of the source will be defined below. After injection to the system, the $`A`$ and $`B`$ particles begin to diffuse. For simplicitly we assume that their diffusion constants are equal to each other, i.e. $`D_A=D_B=D`$. It will be made clear below that such a description is also appropriate to the case of non-equal diffusivities; the calculations in this case will be only essentially more lengthy . Now, the reaction event is defined as follows: When any two $`A`$ and $`B`$ particles approach each other at a fixed separation $`R`$ (the reaction radius), they may enter into reaction forming (an inert with respect to the reaction) reaction product $`O`$. The recombination upon an encounter of $`A`$ and $`B`$ happens with a finite probability $`p`$ (with probability $`q=1p`$ the particles can be reflected) which defines the constant of an elementary reaction act, $`K`$. This constant describes the intrinsic chemical activities of $`A`$ and $`B`$ molecules and is dependent on the nature of the intra- and intermolecular binding forces. In the following we will suppose that this purely ”chemical” constant is known $`a`$ $`priori`$. Besides, we will assume that $`K`$ is large (i.e. the probability of particles reflection from each other is low) and thus will emphasize the ”statistical physics” effects on the reaction kinetics, rather than the effects of chemical constraints. Consequently, all the factors which are exponentially small with $`K`$ will be neglected here.

Now, we define the statistical properties of the particles generation more precisely. Let $`I_A(r,t)`$ and $`I_B(r,t)`$ be the local, at the point with the radius-vector $`r`$, intensities of the production rates of $`A`$ and $`B`$ particles. We take that the volume average values of the production rates obey

$$\frac{1}{V}_V𝑑rI_A(r,t)=\frac{1}{V}_V𝑑rI_B(r,t)=I,$$
(1)
which means that particles generation is steady in time and the mean production rates $`I`$ of $`A`$ and $`B`$ particles are equal to each other.

Defining the correlations in the production rates $`I_{A,B}(r,t)`$ we will consider here two different situations. In the first one (case I), we suppose that $`A`$ and $`B`$ particles are introduced into the reaction bath statistically independent of each other ; that is, the fluctuations of the sources are correlated neither in space, nor in time. In this case, we have

$`{\displaystyle \frac{1}{V}}{\displaystyle _V}𝑑rI_A(r,t)I_A(r+\lambda ,t+\tau )I^2=I\delta (\lambda )\delta (\tau ),(a)`$ (2)
$`{\displaystyle \frac{1}{V}}{\displaystyle _V}𝑑rI_B(r,t)I_B(r+\lambda ,t+\tau )I^2=I\delta (\lambda )\delta (\tau ),(b)`$ (3)
$`{\displaystyle \frac{1}{V}}{\displaystyle _V}𝑑rI_B(r,t)I_A(r+\lambda ,t+\tau )=\mathrm{\hspace{0.33em}0}(c)`$ (4)
In the second case we suppose that $`A`$ and $`B`$ particles are introduced as correlated $`AB`$ pairs***The particles in the pair can, of course, diffuse apart after injection., separated by a fixed distance $`\lambda _g`$ . Such type of external generation may arise in chemical systems in which complex reaction product $`O`$ is continuously forced to break-up by an external radiation (say, laser pulses) into the correlated pairs of the component molecules. Here the radius of pair $`\lambda _g`$ will be mainly determined by the difference of energy ”attributed” to $`O`$ and the energy required to dissociate the reaction product. Another example in which such pairs are produced is the annealing of radiation damage in solids. When the solid is irradiated, atoms are knocked out of their places in the lattice to become interstitials and leave behind a vacancy, and then the vacancies and interstitials diffuse and recombine. In case II, different $`AB`$ pairs are statistically uncorrelated and occur, with an average intensity $`I`$, at random positions in the reaction bath. Then, the fluctuations of the sources obey :

$`{\displaystyle \frac{1}{V}}{\displaystyle _V}𝑑rI_A(r,t)I_A(r+\lambda ,t+\tau )I^2=I\delta (\lambda )\delta (\tau ),(a)`$ (5)
$`{\displaystyle \frac{1}{V}}{\displaystyle _V}𝑑rI_B(r,t)I_B(r+\lambda ,t+\tau )I^2=I\delta (\lambda )\delta (\tau ),(b)`$ (6)
$`{\displaystyle \frac{1}{V}}{\displaystyle _V}𝑑rI_B(r,t)I_A(r+\lambda ,t+\tau )=\gamma _d(\lambda _g)I\delta (|\lambda |\lambda _g)(c)`$ (7)
In Eq.(3.c), the parameter $`\gamma _d(\lambda _g)`$ is the normalization factor which arises because of different possible angular orientations of a given $`AB`$ pair in a $`d`$-dimensional continuum; the value of $`\gamma _d(\lambda _g)`$ depends on the dimensionality of the reaction bath and for $`d=1,2`$ and $`3`$ equals respectively $`1`$, $`(2\pi \lambda _g)^1`$ and $`(4\pi \lambda _g^2)^1`$.

Let $`C_A(r,t)`$ and $`C_B(r,t)`$ denote the local densities of $`A`$ and $`B`$ particles at point with radius-vector $`r`$ at time $`t`$. The time evolution of local densities due to the diffusion of species, their reaction and an external production can be described by the following reaction-diffusion equations :

$`\dot{C}_A(r,t)=`$ $``$ $`\gamma _d(R)K{\displaystyle _V}𝑑r^{}\delta (|rr^{}|R)C_A(r,t)C_B(r^{},t)+`$ (8)
$`+`$ $`D\mathrm{\Delta }_rC_A(r,t)+I_A(r,t),`$ (9)
$`\dot{C}_B(r,t)=`$ $``$ $`\gamma _d(R)K{\displaystyle _V}𝑑r^{}\delta (|rr^{}|R)C_B(r,t)C_A(r^{},t)+`$ (10)
$`+`$ $`D\mathrm{\Delta }_rC_B(r,t)+I_B(r,t),`$ (11)
where the symbol $`\mathrm{\Delta }_r`$ denotes the $`d`$-dimensional Laplace operator acting on the spatial variable $`r`$, and the integration with the delta-function $`\delta (|rr^{}|R)`$ accounts for all possible orientations of an $`AB`$ pair, at which an elementary reaction act can take place.

Now, an experimentally accessible property is not, however, the local density, but rather its volume averaged value

$$C(t)=\frac{1}{V}_V𝑑rC_{A,B}(r,t)$$
(12)
To find an equation which governs the time evolution of $`C(t)`$, let us first represent the local densities in the form

$$C_{A,B}(r,t)=C(t)+\delta C_{A,B}(r,t),$$
(13)
where $`\delta C_{A,B}(r,t)`$ will denote local deviations of particles’ densities from their mean values. By definition,

$$\frac{1}{V}_V𝑑r\delta C_{A,B}(r,t)=\mathrm{\hspace{0.33em}0}.$$
(14)
Then, substituting Eq.(7) into Eqs.(4) and (5) and taking the volume average, we get the following equation

$$\dot{C}(t)=K\left[C^2(t)+G_{AB}(|\lambda |=R,t)\right]+I,$$
(15)
in which $`G_{AB}(\lambda ,t)`$ stands for the pairwise, central correlation function of the form

$$G_{AB}(\lambda ,t)=\frac{1}{V}_V_V𝑑r𝑑r^{}\delta (rr^{}\lambda )\delta C_A(r,t)\delta C_B(r^{},t),$$
(16)
the variable $`\lambda `$ being a $`d`$-dimensional correlation parameter.

Therefore, Eq.(9) shows that the time evolution of the mean particle density is ostensibly coupled to the evolution of the pairwise correlations in the reactive system. Neglecting these correlations, i.e. setting $`G_{AB}(\lambda ,t)=0`$, which is equivalent to the traditional, ”mean-field” assumption that the particles’ spatial distribution is uniform, we obtain the customary, text-book ”law of mass action”. Such an approximation predicts a linear in time growth of mean density at relatively short times, i.e.

$$C(t)It,$$
(17)
and, in the large-$`t`$ limit, an exponentially fast relaxation to the equilibrium density $`C(t=\mathrm{})=(I/K)^{1/2}`$, i.e.

$$C(t)(\frac{I}{K})^{1/2}\left[\mathrm{\hspace{0.33em}1}\mathrm{exp}(2(IK)^{1/2}t)+\mathrm{}\right]$$
(18)
The short-time behavior as in Eq.(11) is quite reasonable and describes the regime in which the particles are merely added into the (initially empty) system by the external source and the reaction between them is negligible, i.e. the regime in which particle density remains very small. As for the analytical prediction in Eq.(12), one may question its validity on intuitive grounds. First, in the system under consideration diffusive motion of particle is the only mechanism to bring particles together and let them react. This motion is essentially $`d`$-dependent and should evidently entail $`d`$-dimensional behaviors, whilst Eq.(12) is independent of the dimensionality of the reaction bath. Second, it shows that with an increase of the chemical reaction constant $`K`$ the equilibrium density tends to zero, which is apparently an artificial behavior. Below we will show that the actual behavior of $`C(t)`$ as $`t\mathrm{}`$ is very different. This turns out to depend essentially on the dimensionality of the reactive system and also on the way how the particles are injected into the system. We show analytically that in the case I, when $`A`$ and $`B`$ particles are introduced into the system statistically independ of each other, in low dimensional systems (i.e. $`d=1,2`$) there occurs a strong reaction-induced spatial organization of particles. Here the absolute value of the pairwise correlation function $`G_{AB}(R,t)`$ (which is negative) grows in time, which induces an unlimited (in absence of hard-core exclusion) growth of mean particles’ densities $`C(t)`$. Therefore, in the case I in low dimensional systems the steady state does not exist, in a striking contradiction to the prediction of Eq.(12). Similar results have been obtained previously in Refs.. In the case I, in three dimensional systems the steady state density is well-defined but, however, turns out to be different from that predicted by Eq.(12). In particular, it is dependent on particles’ diffusion constant, which reflects the pathological behavior of correlations in the reactive system . Actually, we show that correlations of fluctuations in particles local densities are essentially long-ranged and obey, in the steady-state, an $`\mathrm{a}\mathrm{l}\mathrm{g}\mathrm{e}\mathrm{b}\mathrm{r}\mathrm{a}\mathrm{i}\mathrm{c}`$ law $`G_{AB}(|\lambda |,t)1/|\lambda |`$. Finally, we proceed to show that in three dimensional systems with uncorrelated generation of particles the long-time relaxation of mean particles density to its steady-state value is described by a power-law with characteristic exponent $`1/2`$, in contrast to the exponential dependence predicted by Eq.(12). Such a behavior has been first conjectured in Ref. and here will be deduced analytically. For the case II, we show that steady-state density exists in all dimensions . However, its value is also different from that predicted by Eq.(12) and depends, for instance, on the radius of the generated pairs, $`\lambda _g`$. The approach to the steady state in this case is also not exponential in time and is described by a universal algebraic law, reminiscent of the long-time approach to the equilibrium in reversible chemical reactions .

We turn back to Eq.(9) and continue our analysis of the binary reaction kinetics taking into account the influence of pairwise correlations on the time evolution of $`C(t)`$. Omitting the details of the derivation, which can be found in Refs., we write down the system of equations for the time evolution of the pairwise correlation functions

$`\dot{G}_{AB}(\lambda ,t)=`$ $``$ $`KC(t)\left[2G_{AB}(\lambda ,t)+G_{AA}(\lambda ,t)+G_{BB}(\lambda ,t)\right]+`$ (19)
$`+`$ $`\mathrm{\hspace{0.33em}2}D\mathrm{\Delta }_\lambda G_{AB}(\lambda ,t)+I_{AB}(\lambda )+T_{AB}(\lambda ),`$ (20)
$`\dot{G}_{AA}(\lambda ,t)=`$ $``$ $`\mathrm{\hspace{0.33em}2}KC(t)\left[G_{AB}(\lambda ,t)+G_{AA}(\lambda ,t)\right]+`$ (21)
$`+`$ $`\mathrm{\hspace{0.33em}2}D\mathrm{\Delta }_\lambda G_{AA}(\lambda ,t)+I\delta (\lambda )+T_{AA}(\lambda ),`$ (22)
$`\dot{G}_{BB}(\lambda ,t)=`$ $``$ $`\mathrm{\hspace{0.33em}2}KC(t)\left[G_{AB}(\lambda ,t)+G_{BB}(\lambda ,t)\right]+`$ (23)
$`+`$ $`\mathrm{\hspace{0.33em}2}D\mathrm{\Delta }_\lambda G_{BB}(\lambda ,t)+I\delta (\lambda )+T_{BB}(\lambda ),`$ (24)
where $`\mathrm{\Delta }_\lambda `$ denotes the Laplace operator acting on the $`d`$-dimensional variable $`\lambda `$, the symbol $`I_{AB}(\lambda )`$ in Eq.(13) describes the correlations in the production rates of $`A`$ and $`B`$ particles; it is equal to zero in the case I (uncorrelated generation of particles) and to

$$I_{AB}(\lambda )=\gamma _d(\lambda _g)I\delta (|\lambda |\lambda _g)$$
(25)
in case II, when particles are introduced into the system in correlated $`AB`$ pairs. Finally, in Eqs.(13) to (15) the terms $`T_{ij}`$ denote the correlation functions of the third order.

The time evolution of the pairwise correlations is coupled to the evolution of the third-order correlations, which, in turn, depends on the correlations of the fourth order. Thus the non-linearity of the reaction-diffusion Eqs.(4) and (5) entails an infininite hierarchy of equations for correlation functions and one has to resort to some approximate methods.

The most commonly used method invokes truncation of this hierarchy approximating the third-order correlation functions in terms of $`C(t)`$ and $`G_{ij}(\lambda ,t)`$ . Such an approach, as it was first noticed in Ref., results in the Smoluchowski-type approximate results with improved numerical coefficients and is appropriate for the description of the single-species reactions $`A+AO`$, but not for the description of reactions involving two different types of particles. The point is that such an approximation misses an important conservation law, which is specific for $`A+BO`$ reactions. Namely, the reaction process conserves the difference $`Z(r,t)`$ of local densities, $`Z(r,t)=C_A(r,t)C_B(r,t)`$, which changes only due to the diffusion of particles and thus is a pure diffusive mode of the system. Conservation of $`Z(r,t)`$ entails, in turn, the conservation of the combination of pairwise correlation functions, $`S_{}(\lambda ,t)=G_{AA}(\lambda ,t)+G_{BB}(\lambda ,t)2G_{AB}(\lambda ,t)`$, which is also a pure diffusive modeOne may readily verify  that $`T_{AA}+T_{BB}2T_{AB}`$ is exactly equal to zero.. Consequently, only such truncation scheme should correctly describe the behavior of the binary reaction, which does not violate the important conservation laws .

The most simple truncation scheme, which preserves the conservation laws, has been first proposed in Ref.. In this scheme the third-order correlation functions, i.e. $`T_{ij}`$, were set equal to zero. Such a truncation, as it was shown in Refs. and  is equivalent to the assumption that fields $`\delta C_{A,B}(\lambda ,t)`$ have Gaussian distribution. Then, the fourth-order correlation functions automatically decouple into the product of pairwise correlation functions and the third-order correlations are equal to zero. Such an approach leads to, for instance, the correct long-time decay law of the particles mean densities, i.e. the $`t^{d/4}`$-law, but fails to reproduce correctly the intermediate time behaviors; at intermediate times this approach predicts essentially the same behavior as the formal kinetic ”law of mass action” and thus disregards the effects of particles’ diffusion at the intermediate-time stage.

This shortcomming has been revisited and improved in Refs., in which it has been shown that correlation functions of the third order are small only in the limit $`|\lambda |>R`$, while in the domain $`|\lambda |R`$ they are singular and this singularity has an impact on the behavior of the pairwise correlation at the intermediate times. In a discrete-space picture, essential at scales $`|\lambda |R`$, the third-order correlation functions have been computed explicitly ,

$$T_{AA}T_{BB}T_{AB}\gamma _d(R)\dot{C}(t)\delta (|\lambda |R).$$
(26)
Substituting Eq.(17) into Eqs.(13) to (15) one gets then a closed with respect to $`C(t)`$ and $`G_{ij}(\lambda ,t)`$ system of equations. To solve them, it is expedient to represent the pairwise correlations in the form

$$G_{ij}(\lambda ,t)=\widehat{G}_{ij}(\lambda ,t)+g_{ij}(\lambda ,t),$$
(27)
where $`\widehat{G}_{ij}(\lambda ,t)`$ denotes a ”singular” part of the pairwise correlation functions, which accounts merely for the behavior of the third-order correlations, and $`g_{ij}(\lambda ,t)`$ \- the ”fluctuational” part, which accounts for the fluctuation spectrum of the external source and fluctuations stemming out of reaction and diffusive processes.

The ”singular” part of the pairwise correlation functions has been determined in Ref.. In particular, the leading at sufficiently large times behavior of $`\widehat{G}_{ij}(|\lambda |=R,t)`$ have been found to be as follows:

$$\widehat{G}_{ij}(R,t)\dot{C}(t)(\pi t/8D)^{1/2},$$
(28)
in one-dimensional,

$$\widehat{G}_{ij}(R,t)\dot{C}(t)\frac{ln(Dt/R^2)}{8\pi D},$$
(29)
and

$$\widehat{G}_{ij}(R,t)\dot{C}(t)\mathrm{\hspace{0.33em}8}\pi DR,$$
(30)
in two-, and three-dimensional systems, respectively.

Now, inserting Eqs.(19) to (21) to Eq.(9) we obtain the following equation for the time evolution of particles mean density

$$\dot{C}(t)=\frac{KK_S(d)}{K+K_S(d)}\left[C^2(t)+g_{AB}(|\lambda |=R,t)\right]+\frac{I}{1+K/K_S(d)}$$
(31)
where $`K_S(d)`$ obeys, as $`t\mathrm{}`$,

$$K_S(d=1)(\frac{8D}{\pi t})^{1/2},$$
(32)
$$K_S(d=2)\frac{8\pi D}{ln(Dt/R^2)},$$
(33)
and

$$K_S(d=3)\mathrm{\hspace{0.33em}8}\pi DR$$
(34)
One may readily notice that in three-dimensions the $`K_S(d)`$, Eq.(25), coincides exactly with the so-called ”diffusive” Smoluchowski constant; a reaction constant which has been first calculated by Smoluchowski  in his approximate description of the effects of diffusion on the chemical reactions kinetics. This constant accounts for, heuristically, the ”resistivity” of random, diffusive transport of particles with respect to reaction. Employing the Smoluchowski method, the analogues of such a constant have been obtained in Ref. for one- and two-dimensional systems. Remarkably, our results in Eqs.(23) and (24) coincide with those obtained in Refs. and . We note also that the prefactor before the brackets in Eq.(22), i.e. the ratio $`K_{app}=KK_S(d)/(K+K_S(d))`$, is the so-called effective or apparent reaction constant, which was first derived for three-dimensional systems in Ref.. Therefore, an account of the ”singular” part of the third-order correlation function and subsequent extraction of the ”singular” part in the pairwise correlators leads us to the results equivalent to those obtained in terms of the Smoluchowski approach.

Hence, Eq.(12), in which one sets $`g_{AB}(|\lambda |=R,t)=0`$ and $`K_S(d)=\mathrm{}`$ reduces to the formal kinetic ”law of mass action”, while setting $`g_{AB}(|\lambda |=R,t)=0`$ and using $`K_S(d)`$ as in Eqs.(23) to (25), one obtains the effective kinetic equation of the Smoluchowski-type approach. Below, we proceed to show that taking into account the time evolution of the pairwise correlations, i.e. the term $`g_{AB}(|\lambda |=R,t)`$, one arrives at completely different physical behavior as compared to the ones predicted by the formal kinetic and Smoluchowski approaches.

Finally, we obtain the following system of equations, obeyed by the ”fluctuational” part of the pairwise correlation functions. It reads

$`\dot{g}_{AB}(\lambda ,t)=`$ $``$ $`KC(t)\left[2g_{AB}(\lambda ,t)+g_{AA}(\lambda ,t)+g_{BB}(\lambda ,t)\right]+`$ (35)
$`+`$ $`\mathrm{\hspace{0.33em}2}D\mathrm{\Delta }_\lambda g_{AB}(\lambda ,t)+I_{AB}(\lambda ),`$ (36)
$`\dot{g}_{AA}(\lambda ,t)=\mathrm{\hspace{0.33em}2}KC(t)\left[g_{AB}(\lambda ,t)+g_{AA}(\lambda ,t)\right]+\mathrm{\hspace{0.33em}2}D\mathrm{\Delta }_\lambda g_{AA}(\lambda ,t)+I\delta (\lambda ),`$ (37)
$`\dot{g}_{BB}(\lambda ,t)=\mathrm{\hspace{0.33em}2}KC(t)\left[g_{AB}(\lambda ,t)+g_{BB}(\lambda ,t)\right]+\mathrm{\hspace{0.33em}2}D\mathrm{\Delta }_\lambda g_{BB}(\lambda ,t)+I\delta (\lambda )`$ (38)
Equations (26) to (28), accompanied by Eq.(22), are now closed with respect to mean particles’ densities and pairwise correlations, and suffice the computation of the time evolution of the monomer-monomer reaction scheme.

## III Kinetics of the monomer-monomer reaction scheme.

Below we will analyse solutions of Eqs.(22) to (28) in systems of different dimensionalities and with different types of external particle generation. The derivation of results in case of one-dimensional systems will be presented in detail. The steps involved for such a derivation in higher dimensions are essentially the same and here we will merely discuss the results.

### A Low dimensional systems.

Let us start with the case of one-dimensional systems in which an external source produces uncorrelated $`A`$ and $`B`$ particles.

We note first that the system of equations (26) to (28) possesses two integrable combinations

$$S_{}(\lambda ,t)=\mathrm{\hspace{0.33em}2}g_{AB}(\lambda ,t)g_{AA}(\lambda ,t)g_{BB}(\lambda ,t),$$
(39)
which is related to the conserved property $`Z(r,t)`$, and

$$S_+(\lambda ,t)=\mathrm{\hspace{0.33em}2}g_{AB}(\lambda ,t)+g_{AA}(\lambda ,t)+g_{BB}(\lambda ,t)$$
(40)
These integrable combinations obey

$$\dot{S}_{}(\lambda ,t)=\mathrm{\hspace{0.33em}2}D\mathrm{\Delta }_\lambda S_{}(\lambda ,t)\mathrm{\hspace{0.33em}2}I\delta (\lambda ),$$
(41)
which is thus the pure diffusive mode of the system, not affected by the reaction, and

$$\dot{S}_+(\lambda ,t)=\mathrm{\hspace{0.33em}2}D\mathrm{\Delta }_\lambda S_+(\lambda ,t)\mathrm{\hspace{0.33em}4}KC(t)S_+(\lambda ,t)+\mathrm{\hspace{0.33em}2}I\delta (\lambda )$$
(42)
The desired property, i.e. the correlation function $`g_{AB}(\lambda ,t)`$ which enters the Eq.(22), may be then expressed in terms of these integrable combinations as

$$g_{AB}(\lambda ,t)=\frac{1}{4}(S_{}(\lambda ,t)+S_+(\lambda ,t))$$
(43)
Consider now the solutions to Eqs.(31) and (32) in one-dimensional systems. Applying the Fourier transformation over the variable $`\lambda `$,

$$S_\pm (\omega ,t)=\frac{1}{\sqrt{2\pi }}_{\mathrm{}}^{\mathrm{}}𝑑\lambda \mathrm{exp}(i\omega \lambda )S_\pm (\lambda ,t)$$
(44)
to Eqs.(31) and (32), and assuming that at $`t=0`$ no $`A`$ and $`B`$ particles were present in the system, one readily gets that the Fourier-images of the integrable combinations follow

$`S_{}(\omega ,t)`$ $`=`$ $`I\sqrt{{\displaystyle \frac{2}{\pi }}}{\displaystyle _0^t}𝑑\tau exp(2D\tau \omega ^2)=`$ (45)
$`=`$ $`{\displaystyle \frac{I}{D\omega ^2\sqrt{2\pi }}}(1exp(2D\tau \omega ^2)),`$ (46)
and

$$S_+(\omega ,t)=I\sqrt{\frac{2}{\pi }}_0^t𝑑\tau exp(2D\tau \omega ^2\mathrm{\hspace{0.33em}4}K_\tau ^t𝑑\tau ^{}C(\tau ^{}))$$
(47)
Now we notice that in the extreme situation, when reaction act occurs at any encounter of any $`A`$ and $`B`$ particle (i.e. when $`K=\mathrm{}`$) the second integrable combination $`S_+(\omega ,t)`$ vanishes since the integral $`_\tau ^t𝑑\tau ^{}C(\tau ^{})`$ is obviously positively defined. One can show, however, that even for the finite $`K`$s the influence of $`S_+(\omega ,t)`$ on the pairwise correlation function, Eq.(33), is not essential at large times and the dominant contribution to $`g_{AB}`$ comes from $`S_{}(\omega ,t)`$.

We note that setting $`t=\mathrm{}`$ in Eq.(35) we obtain that $`S_{}(\omega ,\mathrm{})`$ has a steady-state spectrum of the form $`S_{}(\omega ,\mathrm{})1/\omega ^2`$, i.e. the spectrum which has an essential singularity when $`\omega 0`$. Such a singular behavior of the fluctuation spectrum of the pairwise correlations in systems with binary reactions followed by an external uncorrelated production of the reactive species has been first obtained, in terms of a different than ours approach, in Refs. and . The authors concluded thus that the steady state of such a system is highly anomalous; since such a singularity is not integrable in low dimensional systems, the steady state values of the integrable combination $`S_{}(\lambda ,t)`$ and thus of the correlation function $`g_{AB}`$ are infinitely large, which means that as time evolves the system progressively coarses into the domains containing particles of only one type.

Consider now how the integrable combination $`S_{}(\lambda ,t)`$ and the correlation function $`g_{AB}`$ grow in time. Taking the inverse Fourier transformation of the first line in Eq.(35) we get

$$S_{}(\omega ,t)=\frac{I}{\sqrt{2\pi D}}_0^t\frac{d\tau }{\sqrt{\tau }}\mathrm{exp}(\lambda ^2/8D\tau )$$
(48)
The integrand in Eq.(37) is a bell-shaped function with its maximum at point $`\tau =\lambda ^2/8D`$. For bounded $`\lambda `$, the bulk contribution to the integral comes from the algebraic tail $`1/\sqrt{\tau }`$ and consequently, the leading at $`tR^2/8D`$ behavior of the integrable combination follows

$$S_{}(|\lambda |=R,t)=I\sqrt{\frac{2t}{\pi D}}$$
(49)
Accordingly, the absolute value of the ”fluctuational” part of the pairwise correlation function grows in time as

$$g_{AB}(|\lambda |=R,t)=I\sqrt{\frac{t}{8\pi D}}$$
(50)
Inserting the just derived expression into the Eq.(22) and noticing that the correct asymptotical behavior of the mean density obtains when the terms in brackets compensate each other, i.e., when

$$C(t)=\sqrt{g_{AB}(|\lambda |=R,t)},$$
(51)
we find that

$$C(t)=I^{1/2}(\frac{t}{8\pi D})^{1/4},$$
(52)
i.e. in one-dimensional systems with random uncorrelated generation of the reactive species the mean particle density grows sublinearly in time as time progresses. The behavior as in Eq.(41) has been also obtained earlier in Refs..

Consider now how the situation will be changed in the case II, when $`A`$ and $`B`$ particles are introduced into the reactive bath as correlated pairs. In this case one readily gets that the Fourier-image of the integrable combination $`S_{}(\lambda ,t)`$ obeys the following equation

$$\dot{S}_{}(\omega ,t)=2D\omega ^2S_{}(\omega ,t)\mathrm{\hspace{0.33em}2}I(1cos(\omega \lambda _g))$$
(53)
whose solution will read

$$S_{}(\omega ,t)=\frac{I(1cos(\omega \lambda _g))}{D\omega ^2\sqrt{2\pi }}(1\mathrm{exp}(2Dt\omega ^2))$$
(54)
One may readily notice a very important feature of Eq.(43); in a striking contrast to the case I, here the steady-state spectrum is not singular in the limit $`\omega 0`$, but tends to a constant value

$$S_{}(\omega 0,t=\mathrm{})=\frac{I\lambda _g^2}{\sqrt{8\pi }D},$$
(55)
which means that $`S_{}(\lambda ,\mathrm{})`$ and hence, $`g_{AB}(\lambda ,\mathrm{})`$ are bounded in systems of any dimensionality, and thus the well-defined steady-state mean density $`C(t=\mathrm{})`$ also exists. We notice, however, that the steady-state pairwise correlation function is proportional to $`\lambda _g^2`$ and thus may increase indefinitely with growth of $`\lambda _g`$. This unbounded growth is, of course, quite consistent with the result in Eq.(39), since the limit $`\lambda _g\mathrm{}`$ corresponds to the case of uncorrelated generation of particles.

Now, the inverse Fourier transformation gives us

$`S_{}(\lambda ,t)`$ $`=`$ $`{\displaystyle \frac{I}{\sqrt{2\pi D}}}{\displaystyle _0^t}{\displaystyle \frac{d\tau }{\sqrt{\tau }}}\{\mathrm{exp}({\displaystyle \frac{\lambda ^2}{8D\tau }})`$ (56)
$``$ $`{\displaystyle \frac{1}{2}}\mathrm{exp}({\displaystyle \frac{(\lambda \lambda _g)^2}{8D\tau }}){\displaystyle \frac{1}{2}}\mathrm{exp}({\displaystyle \frac{(\lambda +\lambda _g)^2}{8D\tau }})\}=`$ (57)
$`=`$ $`{\displaystyle \frac{I\lambda }{4D\sqrt{\pi }}}\{\mathrm{\Gamma }(1/2,{\displaystyle \frac{\lambda ^2}{8Dt}}){\displaystyle \frac{1}{2}}\mathrm{\Gamma }(1/2,{\displaystyle \frac{(\lambda _g\lambda )^2}{8Dt}})`$ (58)
$``$ $`{\displaystyle \frac{1}{2}}\mathrm{\Gamma }(1/2,{\displaystyle \frac{(\lambda _g+\lambda )^2}{8Dt}})\},`$ (59)
where $`\mathrm{\Gamma }(\alpha ,x)`$ denotes the incomplete Gamma function .

Consider now the asymptotic behavior of the pairwise correlation function, Eq.(33), for different values of parameters $`\lambda `$ and $`\lambda _g`$, and different values of time $`t`$.

One readily gets from Eq.(45) that at sufficiently short times, when $`\lambda \lambda _g8Dt`$, the pairwise correlation function obeys

$$g_{AB}(\lambda ,\lambda _g,t)=\frac{3I\lambda _g^2(8Dt)^{3/2}}{8\sqrt{\pi }D\lambda ^4}\mathrm{exp}(\frac{\lambda ^2}{8Dt}),$$
(60)
which shows that correlations drop off as a Gaussian function at large scales.

Now, at short scales, such that $`\lambda \lambda _g`$ and $`\lambda 8Dt`$, and when $`\lambda _g`$ is sufficiently large, $`\lambda _g8Dt`$, we obtain that $`g_{AB}(\lambda ,\lambda _g,t)`$ obeys Eq.(39), which is not a surprising result since at such scales the correlations in the particles’ injection should be irrelevant.

Within the opposite limit, when $`8Dt\lambda \lambda _g`$ the correlator follows

$$g_{AB}(\lambda ,\lambda _g,t)\frac{I(8Dt)^{3/2}}{16\sqrt{\pi }D\lambda ^2}\mathrm{exp}(\frac{\lambda ^2}{8Dt}),$$
(61)
which is reminiscent of the behavior in Eq.(46).

Finally, in the limit when both $`\lambda 8Dt`$ and $`\lambda _g8Dt`$ (and $`\lambda _g>\lambda `$), i.e. in the limit of very long times, we find the following asymptotic expansion

$$g_{AB}(\lambda ,\lambda _g,t)\frac{I(\lambda _g\lambda )}{16D}\left[1\frac{\lambda _g^2}{\lambda \sqrt{\pi Dt}}\mathrm{exp}(\frac{\lambda ^2}{8Dt})+𝒪(1/t)\right],\lambda _g\lambda ,$$
(62)
where the symbol $`𝒪(1/t)`$ signifies that the correction terms decay with time as $`1/t`$.

Equation (48) suffices to derive the large-$`t`$ evolution of the mean particle density in the case of generation by correlated pairs, which reads

$$C(t)\sqrt{\frac{I(\lambda _gR)}{16D}}\left[1\frac{\lambda _g^2}{2R\sqrt{\pi Dt}}+𝒪(1/t)\right],\lambda _gR$$
(63)
Equations (49) reveals two surprising features; first, the steady-state density turns out to be dependent both on the diffusion constant and on the radius of pairs, generated by the source. Such a dependence is, of course, inconsistent with the predictions of the formal kinetic approach, based on the text-book ”law of mass action”. Second, the approach of particles’ densities to their steady-state values obeys a power-law dependence, in a striking contrast to the exponential one predicted both by the formal kinetic and the Smoluchowski approach.

To close this subsection let us briefly consider the behavior of solutions of the reaction-diffusion equations (22), (26) to (28) in two-dimensional systems.

In the case I, we have from Eqs.(31) and (33) that as $`t\mathrm{}`$ the pairwise correlation function grows (by absolute value) as

$$g_{AB}(|\lambda |=R,t)Iln(Dt/R^2),DtR^2,$$
(64)
and consequently, we get from Eq.(40) that in this case at large times the mean particle density exhibits logarithmically slow growth ,

$$C(t)\sqrt{Iln(Dt/R^2)}$$
(65)
Now, in the case II, we obtain that the steady-state exists and $`g_{AB}(|\lambda |=R,\mathrm{})`$ behaves as

$$g_{AB}(|\lambda |=R,\mathrm{})Iln(\lambda _g),$$
(66)
and hence, the steady-state density turns to be a slowly growing function of the radius of the generated pairs,

$$C(t=\mathrm{})\sqrt{Iln(\lambda _g)}$$
(67)
Some analysis shows also that such a steady-state is approached via an algebraic law

$$C(t)C(t=\mathrm{})(Dt)^1,$$
(68)
in contrast to the exponential in time dependence predicted by mean-field descriptions.

### B Three-dimensional systems.

As we have already mentioned, in the case I the steady-state fluctuation spectrum is characterized by an essential singularity of the type $`1/\omega ^2`$ as $`\omega 0`$. In three-dimensional systems such a singularity is integrable, which insures that the steady-state correlations exist and vanish as $`\lambda \mathrm{}`$. Consequently, the steady-state mean particle density $`C(t=\mathrm{})`$ should exist in 3D also in this case. Let us analyse now the form of these correlations. Solving Eq.(31) in 3D we find (up to the correction terms which are exponentially small with $`K`$) that

$$g_{AB}(\lambda ,t=\mathrm{})\frac{I}{8\pi D\lambda },$$
(69)
i.e. $`AB`$ correlations vanish with the distance between particles $`\lambda `$ as $`1/\lambda `$, which shows that in the monomer-monomer catalytic scheme taking place in three dimensional systems the correlations in the steady-state show a quasi-long-range order decaying as the first inverse power of the interparticle distance.

Now, substituting Eq.(55) into the Eq.(22) we find the following expression for the steady-state density in 3D,

$$C(t=\mathrm{})=\sqrt{(\frac{1}{8\pi DR}+\frac{1}{K})I},$$
(70)
which shows that $`AB`$ correlations lead here to an effective renormalization of the reaction constant in the steady-state, i.e. $`C(t=\mathrm{})`$ has the form $`C(t=\mathrm{})=\sqrt{I/K_{app}}`$, where $`K_{app}`$ is the mentioned above apparent reaction constant .

Consider now how such a steady-state is approached at long times. Expanding the solution of Eq.(31) near the steady-state, we have that pairwise correlations approach the steady-state as a power-law,

$$g_{AB}(|\lambda |=R,t)\frac{I}{8\pi DR}\left[1\frac{R}{\sqrt{\pi Dt}}+O(1/t)\right],$$
(71)
which yields, in turn, a power-law relaxation of the mean particle density to the steady-state

$$C(t)C(t=\mathrm{})(Dt)^{1/2}$$
(72)
Therefore, in contrast to low dimensional systems, in three dimensional systems with random uncorrelated generation of the reactive species the essential singularity in the fluctuation spectrum is integrable, correlations vanish with the distance between particles and the steady-state mean particle density exists. However, the steady-state density is different from that predicted by the mean-field ”law of mass action” and shows, in particular, dependence on the particles’ diffusivity $`D`$. Besides, Eq.(58) reveals that here approach to the steady-state is described by a power-law with the characteristic exponent $`1/2`$, which is essentially non-mean-field behavior.

Finally, for the case II we find the following results for the correlation function and mean density. In the steady-state the $`AB`$ correlations are equal to zero for $`\lambda \lambda _g`$ (again, apart from the exponentially small with $`K`$ terms). In the domain $`\lambda <\lambda _g`$ the correlations exist and are described by

$$g_{AB}(\lambda ,t=\mathrm{})\frac{I}{8\pi D\lambda }(1\frac{\lambda }{\lambda _g}),$$
(73)
which reduces to the result in Eq.(55) when $`\lambda _g=\mathrm{}`$. In constrast to the behavior as in Eq.(55), however, the correlations vanish at finite values of the correlation parameter $`\lambda `$.

Now, Eq.(59) yields for the steady-state mean-particle density

$$C(t=\mathrm{})=\sqrt{I(\frac{1}{K}+\frac{1R/\lambda _g}{8\pi DR})},$$
(74)
which is less than the steady-state density in the case I, Eq.(56), due to a factor $`1R/\lambda _g`$, which renormalizes the Smoluchowski constant. Consequently, for $`\lambda _g>R`$ apparent rate constant here takes the form

$$K_{app}=\frac{8\pi DRK}{8\pi DR+(1R/\lambda _g)K}$$
(75)
We find also that such a steady-state is approached via a power-law,

$$C(t)C(t=\mathrm{})(Dt)^{3/2}$$
(76)
which is faster than the approach described in Eq.(58), but still very different from the exponential behavior predicted by mean-field analysis.

## IV Conclusion.

To summarize, we have shown that both the cases I and II the fluctuations effects dominate the kinetics of the monomer-monomer catalytic scheme involving diffusive particles and induce essential departures from the predictions of the mean-field approaches. In the case I, the effects of fluctuation are especially pronounced in low dimensional systems - the steady-state does not exist and mean particle density grow indefinitely in time, in absence of hard-core exclusion between particles. In three dimensions the steady-state exists, but is characterized by very strong interparticle correlations, which, in turn, have a strong impact on the value of the steady-state mean particle density. The steady-state density is different from that predicted by mean-field ”law of mass action”. The approach to this steady-state is described by an anomalous power-law with the characteristic exponent $`1/2`$, which stems from the presence of essential singularity in the steady-state fluctuation spectrum. In the case II, the steady-state fluctuation spectrum and the steady-state mean particle density exist in any dimension, but show an anomalous, non-mean-fields dependence on the particles’ diffusivity and the radius of pairs, generated by the source. Approach to the steady-state follows a universal power-law with the characteristic exponent $`d/2`$, which resembles, apart from the dependence of the prefactors on the system parameters (e.g. constant of the backward reaction) the long-time approach to the equilibrium in reversible chemical reactions . The origin of such a behavior is that the fluctuation spectrum in the steady-state is flat at small values of the wave-vector, i.e. the essential singularity in the steady-state spectrum of fluctuations is screened.

Figure Caption.

Fig.1. Langmuir-Hinshelwood reaction on a two-dimensional catalytic substrate. Black and grey spheres denote particles of $`A`$ and $`B`$ species, respectively; $`(1)`$ describes the situation in which an $`A`$ and a $`B`$ appear within the reactive distance from each other and may enter into reaction.


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# Untitled Document

Vacuum Energy and Casimir Force in a Presence of Skin-depth Dependent Boundary Condition

S.L. Lebedev 111 E-mail: lsl@chuvsu.ru Permanent adress: 428000 Cheboksary, Chuvash I.Ya. Yakovlev State Pedagogical University.

> The vacuum energy-momentum tensor (EMT) and the vacuum energy corresponding to massive scalar field on $`\mathrm{}_t\times [0,l]\times \mathrm{}^{D2}`$ space-time with boundary condition involving a dimensional parameter ($`\delta `$) are found. The dependent on the cavity size $`l`$ Casimir energy $`\stackrel{~}{E}_C`$ is a uniquely determinable function of mass $`m`$, size $`l`$ and ”skin-depth” $`\delta `$. This energy includes the ”bulk” and the surface (potential energy) contributions. The latter dominates when $`l\delta `$. Taking the surface potential energy into account is crucial for the coincidence between the derivative $`\stackrel{~}{E}_C/l`$ and the $`ll`$-component of the vacuum EMT. Casimir energy $`\stackrel{~}{E}_C`$ and the bulk contribution to it are interconnected through Legendre transformation, in which the quantity $`\delta ^1`$ is conjugate to the vacuum surface energy multiplied by $`\delta `$. The surface singularities of the vacuum EMT do not depend on $`l`$ and, for even $`D`$, $`\delta =0`$ or $`\mathrm{}`$, possess finite interpretation. The corresponding vacuum energy is finite and retains known analytical dependence on the dimension $`D`$.

1. Introduction

The determination of vacuum energy of fields confined to finite volumes is the basic part in the calculations of Casimir force as well as of some bag characteristics of hadrons . At the same time the renormalization approach appears to be not unique: the counterterms necessary to make the vacuum energy finite can depend on the cavity size so that the regularization dependence of Casimir energy appears . Concrete calculations for the scalar case and Dirichlet or Neumann boundary condition on a spherical boundary have been performed in the recent papers . General consideration  shows however that at least for these boundary conditions the surface singularities of the vacuum EMT (and, hence, the aforementioned counterterms) can not depend on the size of the cavity. The detection of such dependences in the papers listed above is a consequence of a coincidence between the local (curvature) and global (size) parameters determining the spherical boundary.

We consider the vacuum characteristics of massive scalar field defined on the domain $`\mathrm{}_t\times [0,l]\times \mathrm{}^{D2}`$. In the absence of curvature we introduce ”skin-depth” parameter $`\delta `$  in boundary condition 222We use the system of units where $`\mathrm{}=c=1`$. The signature of metric is $`(+,,,\mathrm{})`$. $`x^\mu =(t,x_1,𝐱_{})`$. Brackets $`[,]_+`$ mean anticommutator.

$$_1\phi (t,0,𝐱_{})=\frac{1}{\delta }\phi (t,0,𝐱_{}),\phi (t,l,𝐱_{})=0$$
$`(1)`$
This boundary condition implies the presence of the surface potential energy

$$\frac{1}{2\delta }d^{D2}𝐱_{}\phi ^2(t,0,𝐱_{})$$
$`(2)`$
in the total hamiltonian of the model. The latter is, as usual, space integral of 00-component of the energy-momentum tensor

$$\stackrel{~}{T}_{\mu \nu }=\frac{1}{2}[_\mu \phi ,_\nu \phi ]_+\frac{1}{2}g_{\mu \nu }(\phi )^2+\frac{1}{2}g_{\mu \nu }m^2\phi ^2+\xi ^\lambda (g_{\mu \nu }[\phi ,_\lambda \phi ]_+g_{\mu \lambda }[\phi ,_\nu \phi ]_+)$$
$`(3)`$
where the last divergence term should be taken with coefficient $`\xi =1/4`$. This is the only value of $`\xi `$ guaranteeing the diagonality of hamiltonian and its conservation .

2. Energy-momentum tensor and energy of vacuum

The normalized solutions of Klein-Gordon-Fock equation have the form:

$$\stackrel{~}{\phi }_k(x)=(2\omega )^{\frac{1}{2}}(2\pi )^{1\frac{D}{2}}\mathrm{exp}[i\omega t+i\mathrm{𝐪𝐱}_{}]\psi _k(x_1),$$
$`(4)`$
where $`\omega =\sqrt{m^2+𝐪^\mathrm{𝟐}+k^2}`$, and the descrete set of functions

$$\psi _k(x)=N_k\mathrm{sin}k(xl),N_k=\left[\frac{l}{2}\left(1\frac{\mathrm{sin}2kl}{2kl}\right)\right]^{1/2}$$
$`(5)`$
represents the resonator modes. Wave number $`k=z/\delta (\stackrel{~}{l}l/\delta )`$ should be determined from the spectral equation

$$\mathrm{\Delta }(z)z^1tgz\stackrel{~}{l}+1=0,$$
$`(6)`$
following from boundary condition (1). The basis of functions (4) is used to define creation-annihilation operators and vacuum state in a standard manner  333It should be noted, however, that canonical quantization of the system (3) for $`\xi =1/4`$ as a system with a higher derivatives, should account for its degeneracy ..

With the help of Cauchy theorem applied to meromorphic function $`\mathrm{\Delta }(z)`$, it is possible to transform the sums over transcendential roots of eq.(6) into corresponding integrals. The scheme of calculation fits in the formula

$$\underset{z_{n\delta }>0}{}\frac{f(z_{n\delta })}{1{\displaystyle \frac{\mathrm{sin}2z_{n\delta }\stackrel{~}{l}}{2z_{n\delta }\stackrel{~}{l}}}}=\frac{\stackrel{~}{l}}{\pi }\underset{0}{\overset{\mathrm{}}{}}f(z)𝑑z\frac{\stackrel{~}{l}}{2\pi i}\underset{0}{\overset{\mathrm{}}{}}\frac{(1t)[f(it)f(it)]}{sht\stackrel{~}{l}+tcht\stackrel{~}{l}}e^{t\stackrel{~}{l}}𝑑t,$$
$`(7)`$
where $`f(z)`$ is a function analitical in the right half-plane, and $`z_{n\delta }(n=1,2,\mathrm{})`$ are the (real) roots of eq.(6). With the use of eq.(7) one could attach the integral representation to the unrenormalized vacuum EMT. The renormalization is reduced to the subtraction of Minkowskian space contribution (D-regularization  supposed):

$$T_{\mu \nu }_M=\frac{\mathrm{\Gamma }(\frac{1D}{2})}{\sqrt{\pi }(4\pi )^{D/2}}_0^{\mathrm{}}𝑑kM^{D3}diag\left[\begin{array}{c}M^2\\ k^2(1D)\\ M^2\end{array}\right],$$
$`(8)`$
$`M(m^2+k^2)^{1/2}`$. The final answer i.e. renormalized EMT of vacuum, looks like

$$\stackrel{~}{T}_{\mu \nu }_{\delta ,l}=\frac{\mathrm{K}_D}{\delta }\underset{\mu }{\overset{\mathrm{}}{}}𝑑t(t^2\mu ^2)^{\frac{D1}{2}}\left\{\frac{(1t)e^{t\stackrel{~}{l}}}{sht\stackrel{~}{l}+tcht\stackrel{~}{l}}diag\left[\begin{array}{c}ch2tx^{}1\\ \frac{t^2(1D)}{t^2\mu ^2}\\ 1ch2tx^{}\end{array}\right]+e^{2tx^{}}diag\left[\begin{array}{c}1\\ 0\\ I\end{array}\right]\right\}.$$
$`(9).`$
$`(D2)`$-dimensional diagonal of $`\stackrel{~}{T}_{\mu \nu }_{\delta ,l}`$ corresponding to $`𝐱_{}`$ contains expressions of the same type. The following notations were used in eq.(9):

$$\mathrm{K}_D=\frac{\delta ^{1D}}{2(4\pi )^{\frac{D1}{2}}\mathrm{\Gamma }\left(\frac{1+D}{2}\right)},\mu =m\delta ,x^{}=(lx_1)/\delta .$$
$`(10)`$
The energy of vacuum could be determined directly, without resort to eq.(9), as a sum of half-frequences interpreted e.g. with the help of zeta-regularization method . At the same time, Green function method  used to obtain vacuum energy should rely on the tensor $`\stackrel{~}{T}_{\mu \nu }`$ (3) , but not its first three terms

$$T_{\mu \nu }=\frac{1}{2}[_\mu \phi ,_\nu \phi ]_+\frac{1}{2}g_{\mu \nu }(\phi )^2+\frac{1}{2}g_{\mu \nu }m^2\phi ^2.$$
$`(11)`$
$`11`$-component of tensor (3) gives Casimir pressure $`P=\stackrel{~}{T}_{11}_{\delta ,l}`$ which, because of translational symmetry, coincides with $`T_{11}_{\delta ,l}`$ (i.e. the divergence term in (3) does not affect the pressure). The role of divergence term is evident from the fact that value $`\xi =1/4`$ is the only one at which equality

$$\frac{\stackrel{~}{E}_{vac}}{l}=\stackrel{~}{T}_{11}_{\delta ,l}$$
$`(12)`$
holds. Notice that conservation of the total energy  and equality (12) both rely on the value $`\xi =1/4`$.

In proving the eq.(12) it is essential that vacuum energy per unit area of the boundary

$$\stackrel{~}{E}_{vac}=_{x_0}^{ly_0}𝑑x_1\stackrel{~}{T}_{00}_{\delta ,l}=\stackrel{~}{E}_C(l,\delta )+\stackrel{~}{E}_{w1}(x_0,\delta )+\stackrel{~}{E}_{w2}(y_0,0)+\mathrm{},$$
$`(13)`$
where dots denote terms vanishing at $`x_0,y_00`$ as well as at $`l\mathrm{}`$. Only finite part of $`\stackrel{~}{E}_{vac}`$, i.e. Casimir energy

$$\stackrel{~}{E}_C(l,\delta )=\mathrm{K}_D\underset{\mu }{\overset{\mathrm{}}{}}𝑑t\frac{(t^2\mu ^2)^{\frac{D1}{2}}e^{t\stackrel{~}{l}}}{sht\stackrel{~}{l}+tcht\stackrel{~}{l}}\left[\stackrel{~}{l}(t1)\frac{1}{t+1}\right],$$
$`(14)`$
depends on the size of the domain and vanishes when $`l\mathrm{}`$. Boundary divergences are present in r.h.s. of eq.(13) in the form of the energies of the walls, $`\stackrel{~}{E}_{w1,2}`$. For example,

$$\stackrel{~}{E}_{w1}(x_0,\delta )=\mathrm{K}_D\mu ^{D1}\underset{1}{\overset{\mathrm{}}{}}\frac{d\xi }{2\xi }(\xi ^21)^{\frac{D1}{2}}\frac{1\mu \xi }{1+\mu \xi }e^{2mx_0\xi }.$$
$`(15)`$
The specific representation of energies $`\stackrel{~}{E}_{w1,2}`$ depends on regularization employed, but Casimir energy is independent of the latter. Notice that the terms discarded in the r.h.s. of eq.(13) have the property of ”double vanishing” (with respect to limits of $`x_0,y_0`$ and $`l`$) so that energies $`\stackrel{~}{E}_{w1,2}`$ of the walls are determined uniquely within the given regularization scheme.

By a complete analogy with $`\stackrel{~}{E}_{vac}`$, one can find its bulk ($`E_{vac}`$) and surface ($`\mathrm{\Pi }_{vac}=\stackrel{~}{E}_{vac}E_{vac}`$) components, the first dertermined with the help of density $`T_{00}`$ (11). For either of these components the expansion of the form (13) exists giving rize to $`E_C(l,\delta )`$ and $`\mathrm{\Pi }_C(l,\delta )`$ correspondingly. For example,

$$\mathrm{\Pi }_C(l,\delta )=\mathrm{K}_D(1D)\underset{\mu }{\overset{\mathrm{}}{}}𝑑t\frac{t^2(t^2\mu ^2)^{\frac{D3}{2}}e^{t\stackrel{~}{l}}}{(t+1)(sht\stackrel{~}{l}+tcht\stackrel{~}{l})},$$
$`(16)`$
and $`E_C=\stackrel{~}{E}_C\mathrm{\Pi }_C`$. Since $`\mathrm{\Pi }_C(l,\delta )0`$, derivative $`E_C/l`$ does not coincide with the Casimir pressure (12). Nevertheless,

$$\delta \frac{\stackrel{~}{E}_C}{\delta }=\mathrm{\Pi }_C,$$
$`(17)`$
and, with the notations $`\lambda =\delta ^1,f=\mathrm{\Pi }_C/\lambda `$, one finds that $`\stackrel{~}{E}_C`$ and $`E_C`$ are interconnected through Legendre transformation:

$$\stackrel{~}{E}_C(l,\lambda )=E_C(l,f(l,\lambda ))+\lambda f(l,\lambda ),$$
$`(18)`$
so that

$$\left(\frac{E_C}{l}\right)_f=\left(\frac{\stackrel{~}{E}_C}{l}\right)_\lambda ,\mathrm{and}\left(\frac{E_C}{f}\right)_l=\lambda .$$
$`(19)`$
Now energy $`E_C`$ determines the Casimir pressure but under specific condition of constancy of the quantity $`f`$ being one half the ”Casimir” part of $`\phi (0)^2`$, see (2).

3. Asymptotic properties

For the purpose of comparison with electrodynamics, here we consider a massless case. The behaviour of integral (14) in Dirichlet ($`\delta l`$) and Neumann ($`\delta l`$) regimes is displayed by the following expansions ($`m=0`$):

$$\stackrel{~}{E}_C(l,\delta )=\mathrm{K}_D\frac{\zeta (D)\mathrm{\Gamma }(D)}{(2\stackrel{~}{l})^{D1}}\left[1+C_{D1}^1\stackrel{~}{l}^1C_D^2\stackrel{~}{l}^2+C_{D+1}^3\left(1+\frac{\zeta (D+2)}{2\zeta (D)}\right)\stackrel{~}{l}^3\right],$$
$`(20)`$
$$\stackrel{~}{E}_C(l,\delta )=\mathrm{K}_D\stackrel{~}{l}^{D+1}\{\begin{array}{c}A_D(D1)A_{D2}\stackrel{~}{l},D=3,4,\mathrm{},\hfill \\ \\ A_2+\stackrel{~}{l}ln(4\gamma _E\stackrel{~}{l}/\pi )\stackrel{~}{l},D=2.\hfill \end{array}$$
$`(21)`$
Here $`C_n^m`$ denotes binomial coefficient, $`A_D=2^{1D}(12^{1D})\mathrm{\Gamma }(D)\zeta (D)`$, $`ln\gamma _E=0.577`$, and eq.(21) contains the leading corrections only. The expansion of pressure $`\stackrel{~}{T}_{11}_{\delta ,l}`$ corresponding to (20) has the form ($`\delta l)`$:

$$\begin{array}{c}\stackrel{~}{T}_{11}_{\delta ,l}=\frac{(D1)\mathrm{\Gamma }(D)\zeta (D)}{(4\pi )^{\frac{D1}{2}}\mathrm{\Gamma }\left(\frac{1+D}{2}\right)}(2l)^D\times \\ \\ \times \left[1+C_D^1\stackrel{~}{l}^1C_{D+1}^2\stackrel{~}{l}^2+C_{D+2}^3\left(1+\frac{\zeta (D+2)}{2\zeta (D)}\right)\stackrel{~}{l}^3+\mathrm{}\right],\end{array}$$
$`(22)`$
and for Neumann regime (21)

$$\stackrel{~}{T}_{11}_{\delta ,l}=\frac{(D1)l^D}{2(4\pi )^{\frac{D1}{2}}\mathrm{\Gamma }\left(\frac{D+1}{2}\right)}\left[A_D(D2)A_{D2}\stackrel{~}{l}+\mathrm{}\right].$$
$`(23)`$
The four terms in the square brackets of eq.(22) (term with $`\zeta `$-functions excluding) could be obtained through the Taylor series for $`(l+\delta )^D`$. Thus, eq.(22) demonstrates the role of $`\delta `$ as penetration depth . Unlike Dirichlet case (22), the correction term in the brackets of eq.(23) emerges due to surface energy $`\mathrm{\Pi }_C`$ only. Numerical analysis of the formulas (14) and (16) taken at $`m=0`$ shows the dominance of the surface contribution $`\mathrm{\Pi }_C`$ over the bulk one ($`E_C`$) in the region $`l(1÷4)\delta `$. The difference in signs between those quantities is responsible for the shift of the position of the minimum from $`l4.5\delta `$ (for $`E_C`$) to $`l1.8\delta `$ (for $`\stackrel{~}{E}_C`$). At that time, the qualitative behaviours of energies $`E_C`$ and $`\stackrel{~}{E}_C`$ as functions of $`l`$ are alike showing a typical van-der-vaals character.

At $`D=4`$ formula (22) takes the form

$$\stackrel{~}{T}_{11}_{\delta ,l}=\frac{\pi ^2}{480l^4}\left[1+4\frac{\delta }{l}10\frac{\delta ^2}{l^2}+20\left(1+\frac{9\pi ^2}{185}\right)\frac{\delta ^3}{l^3}+\mathrm{}\right],$$
$`(24)`$
and should be compared with the corresponding expression in the case of electromagnetic field confined to the region between impedance walls ($`\delta `$\- skin-depth parameter):

$$P=\frac{\pi ^2}{240l^4}\left[1+\frac{16}{3}\frac{\delta }{l}24\frac{\delta ^2}{l^2}+\frac{640}{7}\left(1+\frac{9\pi ^2}{740}\right)\frac{\delta ^3}{l^3}+\mathrm{}\right].$$
$`(25)`$
Formula (25) except the last term $`\delta ^3/l^3`$ in the square brackets, was extracted from . The corresponding coefficients of expansions (25) and (24) are related to each other in ratios 1, 1.33, 2.4, 3.46, hence showing the growing effect of spin when going deeper into the boundary.

4. Interpretation of surface singularities at $`\delta =0`$ and $`\mathrm{}`$

The surface singularities of the vacuum EMT is a stumbling-block problem for any field theory expected to establish the connection between its local properties and observational predictions . It is shown below that the method of dimensional regularization could be applied not only to interpret the singular sums like $`E_{vac}=\underset{\nu }{}\frac{1}{2}\omega _\nu `$, but gives a reasonable finite answer for the energy density of vacuum as well. The method works for even $`D,\delta =+0`$ 444The singular nature of Dirichlet limit (contrary to Neumann one) is explained in . or $`\mathrm{}`$ and leads to an energy expression consistent with the one of $`\zeta `$-regularization method.

Boundary divergences are represented in r.h.s. of eq.(13) by the energies of the walls ($`\stackrel{~}{E}_{w1,2}`$). Correspondingly, we consider 00-component of a tensor (9) in the limit $`l\mathrm{},\delta =+0`$ (alternative case $`\delta =\mathrm{}`$ differs from (26) only in sign):

$$\stackrel{~}{T}_{00}_{0,\mathrm{}}=\left(\frac{m^2}{2\pi }\right)^{{\scriptscriptstyle \frac{D}{2}}}\{\begin{array}{c}\rho ^{D/2}K_{D/2}(\rho ),0<\rho \underset{}{<}1,x/l0;\\ \\ (\rho ^{})^{D/2}K_{D/2}(\rho ^{}),0<\rho ^{}\underset{}{<}1,x^{}/l0\end{array}$$
$`(26a,b)`$
($`\rho =2mx,\rho ^{}=2mx^{}=2m(lx)`$). Exploiting recurrence relations between modified Bessel functions $`K_\nu (\rho )`$ , let us transform energy density (26a):

$$\stackrel{~}{T}_{00}_{0,\mathrm{}}\stackrel{~}{T}_{00}_{0,\mathrm{}}\frac{d}{d\rho }f_D(\rho )=\left(\frac{m^2}{2\pi }\right)^{{\scriptscriptstyle \frac{D}{2}}}\frac{\rho ^{1ϵ}K_{ϵ1}(\rho )}{(1D)(3D)\mathrm{}(12ϵ)}.$$
$`(27)`$
Here $`ϵ\frac{D}{2}n0,n=1,2,\mathrm{}`$, and function

$$f_D(\rho )=\left(\frac{m^2}{2\pi }\right)^{{\scriptscriptstyle \frac{D}{2}}}\left[\frac{\rho ^{1\frac{D}{2}}K_{\frac{D}{2}}(\rho )}{1D}+\frac{\rho ^{2\frac{D}{2}}K_{\frac{D}{2}1}(\rho )}{(1D)(3D)}+\mathrm{}+\frac{\rho ^{1ϵ}K_ϵ(\rho )}{(1D)(3D)\mathrm{}(12ϵ)}\right]$$
$`(28)`$
possesses following properties: $`i)`$ for $`\mathrm{}\mathrm{e}D<0`$ ($`\mathrm{}\mathrm{e}ϵ<n`$)

$$f_D(0)=f_D(\mathrm{})=0,$$
$`(29)`$
so that divergence addition in the l.h.s. of eq.(27) does not affect the vacuum energy of the wall

$$\stackrel{~}{E}_{w1}(0,0)=\left(\frac{m^2}{2\pi }\right)^{{\scriptscriptstyle \frac{D}{2}}}_0^{\mathrm{}}𝑑x\rho ^{D/2}K_{D/2}(\rho )=\frac{m^{D1}\mathrm{\Gamma }\left(\frac{1D}{2}\right)}{8(4\pi )^{\frac{D1}{2}}}.$$
$`(30)`$
(the vacuum energy of Neumann wall $`\stackrel{~}{E}_{w1}(0,\mathrm{})=\stackrel{~}{E}_{w1}(0,0)=E_{w1}(0,0)`$);

$`ii)`$ a term $`f_D^{^{}}(\rho )`$ in the l.h.s. of eq.(27) taken at ”physical” values of $`D=2,4,6,\mathrm{}`$, acts as a counterterm eliminating all nonintegrable singularities of density (26a);

$`iii)`$ this counterterm preserves an exponential decreasing behaviour of the modified density (27) at $`x>\mathrm{}/mc`$. The latter is not still uniquely defined: one can add to $`f_D(\rho )`$ any regular function having the property (29) (see ).

Thus, at $`\delta =+0`$ the total energy of vacuum includes Casimir part

$$\stackrel{~}{E}_C(l,0)=\frac{m^Dl}{(4\pi )^{\frac{D1}{2}}\mathrm{\Gamma }(\frac{D+1}{2})}\underset{1}{\overset{\mathrm{}}{}}𝑑\xi \frac{(\xi ^21)^{\frac{D1}{2}}}{e^{2\xi ml}1}$$
$`(31)`$
and doubled topological (according to ) energy (30) caused by the presence of the edge of the manifold. At $`\delta =\mathrm{}`$ the total energy of vacuum reduces to $`\stackrel{~}{E}_C(l,\mathrm{})`$ because the energies of Neumann ($`x=0`$) and Dirichlet ($`x=l`$) walls cancell out. Energy $`\stackrel{~}{E}_C(l,\mathrm{})=E_C(l,\mathrm{})`$. The integral representation for it can be obtained from (31) by substitution ”$`+`$” for ”$``$” in the denominator of the integrand and by multiplying the whole expression by $`(1)`$.

Dimensional regularization method does not result in satisfactory expressions for the vacuum energy when $`0<\delta <\mathrm{}`$. As it may be seen from eq.(15) (taken at $`x_0=0`$), for even $`D`$ the corrections of order $`\mu ,\mu ^2,\mathrm{}`$ to the energy (30) cannot be interpreted in the way like (30). On the other hand, for odd $`D3`$ the energy (30) is infinite. Now, the depending on $`\mu `$ ”corrections” find finite interpretation, but being summed up, they lead to logarithmic divergence in the Neumann limit $`\mu \mathrm{}`$.

The analytical structure of the surface singularities of the vacuum EMT (26) with respect to dimension $`D`$ is just that property which makes dimensional regularization applicable to define finite density (27). In view of the absence of translational symmetry it seems quite natural for density like (27) to exist. At that time finite renormalization of the type suggested in  eliminates the energy of the walls from $`\stackrel{~}{E}_{vac}=\stackrel{~}{E}_C(l,0)+2\stackrel{~}{E}_w`$. This procedure needs in explaination how to interpret the expressions like (27). It should be mentioned in addition that the energy density (27) (but not (26)) vanishes when $`m=0`$. This disappearance was assumed to be characteristic of conformally invariant models .

5. Conclusion

Below some comments on literature related to the present topic are given. The massless case for the scalar model at hand (dimension $`D=2,3`$) was considered in works  and formulas consistent with (9) ( $`D=3,m=0`$, ) and (14) ( $`D=2,m=0`$, ) were derived. The work  exploits an idea  of replacement of the boundary with a singular non-locally regularized potential, that occured to be equivalent to taking potential energy (2) into account.

Formula (2.18) from  corresponds to our formula (31). Doubled energy (30) appears in  as well, but it was not associated there with the vacuum energy of half-space. Our formula (9) at $`\delta =+0`$ (or, equivalently, (31) and (12)) gives the expression

$$\begin{array}{c}\stackrel{~}{T}_{11}_{0,l}=\frac{m^D(1D)}{(4\pi )^{\frac{D1}{2}}\mathrm{\Gamma }\left(\frac{1+D}{2}\right)}\underset{1}{\overset{\mathrm{}}{}}\frac{\xi ^2(\xi ^21)^{\frac{D3}{2}}}{e^{2ml\xi }1}𝑑\xi |_{ml1}=\\ \\ =\frac{m^D}{(4\pi ml)^{\frac{D1}{2}}}e^{2ml}\left[1+\frac{(D1)(D+5)}{16ml}+\mathrm{}\right],\end{array}$$
$`(32)`$
which does not coincide with formula (2.13) from . The latter, being taken at zero temperature, includes physically unacceptable dependence of pressure on (arbitrary) renormalization parameter. Such dependence, as it was noted above, is characteristic of curved boundary under the condition of coincidence between the parameters determining its curvature and size.

The author would like to acknowledge useful discussions with A.I. Nikishov and V.I. Ritus and financial support from RFFR (grants 95-02-04219-a and 96-15-96463).

References


text:
# Evolution of the universality class in slightly diluted (1>𝑝>0.8) Ising systems.

## Abstract

The crossover of a pure (undiluted) Ising system (spin per site probability $`p=1`$) to a diluted Ising system (spin per site probability $`p<0.8`$) is studied by means of Monte Carlo calculations with $`p`$ ranging between 1 and 0.8 at intervals of 0.025. The evolution of the self averaging is analyzed by direct determination of the normalized square widths $`R_M`$ and $`R_\chi `$ as a function of $`p`$. We find a monotonous and smooth evolution from the pure to the randomly diluted universality class. The $`p`$-dependent transition is found to be indepent of size ($`L`$). This property is very convenient for extrapolation towards the randomly diluted universality class avoiding complications resulting from finite size effects.

Systems with quenched randomness have been studied intensively for several decades . One of the first results was establishing the so called Harris criterion , which predicts that a weak dilution does not change the critical behavior’s character near second order phase transitions for systems of dimension $`d`$ with specific heat exponent lower than zero (the so called P systems), $`\alpha _{pure}<0\nu _{pure}>2/d`$ due to the hyperscaling relationship, in the undiluted case. This criterion has been confirmed by several renormalization group (RG) analyses , and by scaling analysis . It was shown to hold also in strongly diluted systems by Chayes et al. . For $`\alpha _{pure}>0`$ (the so called R systems), for example the Ising 3D case, the system fixed point flows from that of a pure (undiluted) fixed point towards a new stable fixed point at which $`\alpha _{random}<0`$  for diluted systems.

Recently Ballesteros et al. have used the Monte Carlo approach to study diluted Ising systems in two, three  and four dimensions . The existence of a new universality class for the randomly diluted Ising system (RDIS) (different from that of the pure Ising model, and $`p`$-independent being $`p`$ the spin per site probability) is proved using an infinite volume extrapolation technique based upon the leading correction to scaling. The critical exponents obtained this way agree with the experimental critical exponents for a random disposition of vacancies in diluted magnetic systems .

The crossover from the pure Ising system $`p=1`$ to the randomly diluted system may occur for very large values of the average density of occupied sites ($`1>p>0.8`$), i.e. systems with a very small amount of vacancies. In this region, the specific heat critical exponent must flow from a value grater than zero, $`\alpha _{pure}>0`$ for $`p=1`$, to a value smaller than zero, $`\alpha _{random}<0`$ for $`p=0.8`$. It means that in principle is possible to expect the existence of a critical density $`p_c`$ at which its value is equal to zero. The $`p_c`$ value has been found to be around $`0.9`$ .

In principle it is not clear whether this crossover should occur smoothly or whether the crossover should take place sharply at a critical value $`p_c,`$ separating the two distinct universality classes. This is a crucial question to establish whether the slightly diluted systems should be considered as pure (basically undiluted), as randomly diluted systems, or, on the contrary, as intermediate states between both extreme classes. There is an intrinsic difficulty in detecting the evolution of critical exponents from pure to diluted random Ising systems due to the fact that they are very similar (see Table I). Following Ballesteros et al. we find $`\alpha _{random}=0.051,\beta _{random}=0.3546,\gamma _{random}=1.342`$ in comparison with the pure undiluted values: $`\alpha _{pure}=0.11,\beta _{pure}=0.3267,\gamma _{pure}=1.237`$  (incidentally, this does not happen if the disorder is long range correlated ). That is why it is useful to study some other universal quantity which clearly indicates the difference between the pure and the random universality classes.

For a random hypercubic sample of linear dimension $`L`$ and number of sites $`N=L^d`$, any observable singular property $`X`$ presents different values for different random realizations corresponding to the same average dilution. This means that X behaves as a stochastic variable with average $`[X]`$, variance $`(\mathrm{\Delta }X)^2`$ and a normalized square width $`R_X=(\mathrm{\Delta }X)^2/[X]^2`$. This quantity allows us to determine properly the evolution from the pure to the randomly diluted system by an investigation of its self averaging behavior. A system is said to exhibit self averaging (SA) if $`R_X0`$ as $`L\mathrm{}`$. If the system is away from criticality, $`L>>\xi `$ (being $`\xi `$ the correlation length) the central limit theorem indicates that strong SA must be expected. However, the self-averaging behavior of a ferromagnet at criticality (where $`\xi >>L)`$ is not so obvious. This point has been studied recently. Wiseman and Domany (WD) have investigated the self-averaging of diluted ferromagnets at criticality by means of finite-size scaling calculations, concluding weak SA for both the P and R cases. In contrast Aharony and Harris (AH), using a renormalization group analysis in $`d=4\epsilon `$ dimensions, proved the expectation of a rigorous absence of self-averaging in critically random ferromagnets . More recently, Monte Carlo simulations where used to check this lack of self-averaging in critically disordered magnetic systems . The absence of self-averaging was confirmed. The source of the discrepancy with previous scaling analysis by WD was attributed to the particular size ($`L`$) dependence of the distribution of pseudocritical temperatures used in their work.

In the present work we study the evolution of the normalized square width from $`p=1`$ to $`p=0.8`$ at small steps $`\mathrm{\Delta }p=0.025,`$ in an effort to characterize in detail the evolution of the normalized square width from $`R_M=R\chi =0`$ to the zone where lack of self-averaging $`(R_M0`$ and $`R\chi 0)`$ appears. We will determine whether there is some sharp critical value $`p_c`$ separating both universality classes, or there is a smooth evolution. We have performed Monte Carlo calculations using the Wolff single cluster algorithm  in diluted three dimensional Ising systems at criticality for different values of the site occupation spin probability $`1>p>0.8.`$ In order to obtain good enough statistics in our determination of the normalized square width for magnetization and susceptibility, we have used 500 samples for the sizes $`L=20,40,60.`$ The magnetization and susceptibility of each sample was determined using 50.000 MCS leaving the previous 100.000 MCS for thermalization. The critical temperature for each dilution was taken by interpolation between the data reported by Heuer et al.  and Ballesteros et al. . We may note that there are no much data in the literature about the critical temperature in this region of slightly diluted systems. A ”nearly-linear” extrapolation of the data for $`T_c`$ vs. $`p`$ from $`p=1`$ to $`p=0.8`$ seems clear from Fig.1. To check this we have calculated the critical temperature for several values of $`p`$ by means of statistics on the Binder Cumulant, and we have found that the data lie over the interpolation functions previously considered.

We can build histograms with the values obtained for susceptibility or magnetization at criticality. In the case of very high $`p`$ values, corresponding to very-low dilution, the width of these histograms is very small, indicating the existence of proper self-averaging. However, for somewhat lower values of $`p`$, the system starts its crossover to the randomly diluted behavior and the width of the histograms begins to increase, indicating that lack of self-averaging is taken place. Fig.2a and b show the evolution of these histograms for the case of the susceptibility and for $`L=60`$. Note that the width of the histograms increases monotonously as $`p`$ decreases, indicating a smooth flow towards the random diluted universality class. We will see this point more clearly studying the value of the normalized square width.

The results obtained for the normalized square width of the magnetization and the susceptibility are presented in Fig3 and Fig4 respectively. Note how in both cases we find a smooth evolution indicating that the crossover from the pure fixed point to the randomly diluted fixed point takes place smoothly and continuously and that there is no apparent critical value of $`p_c`$ acting as a boundary between the two regimens.

The value of the normalized square width for a given $`p`$, can be strongly affected by finite size effects. In order to obtain a value of $`R_M`$ or $`R_\chi `$ independent of $`p`$ for $`p<0.8`$ it is necessary to consider very high values of $`L`$  or to use the so called infinite volume extrapolation . However, for small dilution $`(1>p>0.8)`$ the values of the normalized square width are nearly unaffected by finite size effects , but they are dependent of $`p`$. That is the reason why in Fig3 and Fig4 all the data seem to collapse over the same curve. This does not happen for $`p<0.8`$ where finite size effects clearly appear. To show this, we present in Fig5 data for the susceptibility together with data by Ballesteros et al.  for different values of $`L`$ and for values of $`p<0.8.`$ Note that the tendency of the data for $`L\mathrm{}`$, seems to be towards $`R_\chi (p=0.8)`$. It means that the effect of the finite size is to introduce a apparent increase in the value of the normalized square width which should not exist for the sample with $`L=\mathrm{}`$. If we consider the data in the $`p`$-dependent zone, that is $`1>p>0.8`$, where there is small $`L`$ dependence, we can make and extrapolation to $`pp_p`$ (being $`p_p`$ the probability for which the system suffers percolation: $`p_p0.31`$) that is not going to be affected by finite size effects. In our case we have used a hyperbolic tangent to fit our data, $`R_\chi (L,1p)=R_\chi (\mathrm{})tanh[const(1p)]`$, leaving free the universal value of the normalized square width $`R_\chi (\mathrm{})`$ and the slope constant ($`const)`$. Results are shown in Fig5. For $`L=40,60`$ we find a p-independent universal value $`R_\chi (\mathrm{})0.155`$, very close to previously reported values : $`0.150(7)`$ . For $`L=20,`$ on the other hand, finite size effects are important even in the region $`(1>p>0.8)`$, and the extrapolation gives a somewhat higher value $`R_\chi (\mathrm{})0.19`$.

In conclusion, we have presented Monte Carlo data for diluted Ising systems in the region where crossover to the diluted random universality class takes place $`(1>p>0.8).`$ The evolution of the normalized square width for the magnetization $`R_M`$ and the susceptibility $`R_\chi `$ indicates a smooth transition with no critical probability $`p_c`$ (corresponding to a well defined boundary between the pure and the randomly diluted universality classes). The transition zone studied is $`p`$-dependent but $`L`$-independent. This result is very convenient for extrapolation to the universal value $`R_\chi (\mathrm{})`$ which is independent of $`L.`$

We acknowledge financial support from CGCyT through grant PB96-0037.

Figure Captions

Fig1: Critical temperature vs. spin per site probability in the slightly diluted zone. Our data is compared with the extrapolation performed for data by Heuer et al.  and Ballesteros et al. .

Fig2: Normalized histograms for the susceptibility values obtained at criticality. The values of the spin per site probability considered are (a) 0.8,0.825,0.85, 0.875 and (b) 0.9,0.925,0.95,0.975.

Fig3: Normalized square width for the magnetization vs. $`1p`$, for values of $`L=20,40,60`$. Dotted line is just a guide for the eye.

Fig4: Normalized square width for the susceptibility vs. $`1p`$, for values of $`L=20,40,60`$. Dotted line is just a guide for the eye.

Fig5: Normalized square width for the susceptibility vs. $`1p`$ for values of $`L=20,40,60`$ (circles), together with the data reported in . The two continuous lines indicate the universal value of $`R_\chi `$ for the randomly diluted Ising system reported in . The hyperbolic extrapolation of the data is indicated by a segmented line for $`L=40,60`$ and by a doted line for $`L=20`$.


text:
# ON THE EFFECTIVE LIGHT-CONE QCD-HAMILTONIAN

## 1 Introduction

The bound-state problem in a field theory particularly gauge field theory is a very difficult many-body problem and has not been solved thus far. But perhaps an exact solution is not necessary for reconciling the so succesful constituent quark models with a covariant theory such as QCD and for being able to compute observables like the structure functions and distribution amplitudes from an underlying theory. Perhaps it suffices to have approximate or QCD-inspired solutions which are not wrong from the outset. The present work is still ongoing and contributes to these questions. Perhaps one begins to understand the essential point.

## 2 A QCD-inspired effective interaction

The light-cone approach to the bound state problem aims at diagonalizing the invariant mass-squared operator.$`^\mathrm{?}`$ Its matrix elements are obtained directly from the gauge field Lagrangian in the light-cone gauge and are explicitly tabulated.$`^\mathrm{?}`$ The many-body aspect of the problem was reduced recently, by the method of iterated resolvents,$`^\mathrm{?}`$ to the problem of phrasing an effective Hamiltonian which acts only in the Fock space of one quark and one anti-quark. The reduction is not exact but rests on certain simplifying assumptions which can be checked only a posteriori. Quite cautiously, one should therefore speak of a ‘QCD-inspired’ effective Hamiltonian. Important is that both the effective and the full Hamiltonian have in principle the same eigenvalue spectrum and that the Fock space is systematically reduced to the $`q\overline{q}`$-space. Important is also that the Fock-space is not truncated, that all Lagrangian symmetries are preserved, and that the higher Fock-space amplitudes can be retrieved systematically from the $`q\overline{q}`$-projection once that is available.

The effective interaction has several contributions which are illustrated in Fig. 1. The present work is restricted to flavor-off-diagonal mesons, to mesons where quark and anti-quark have different flavors. Then the effective interaction due to the annihilation of two gluons is kinematically suppressed, and the final (one-body) integral equation in the $`q\overline{q}`$-space is governed by an effective one gluon exchange, i.e.

$`M^2x,\stackrel{}{k}_{};\lambda _1,\lambda _2|\psi =\left[{\displaystyle \frac{\overline{m}_1^2+\stackrel{}{k}_{}^{\mathrm{\hspace{0.17em}2}}}{x}}+{\displaystyle \frac{\overline{m}_2^2+\stackrel{}{k}_{}^{\mathrm{\hspace{0.17em}2}}}{1x}}\right]x,\stackrel{}{k}_{};\lambda _1,\lambda _2|\psi `$
$`{\displaystyle \frac{1}{4\pi ^2}}{\displaystyle \underset{\lambda _q^{},\lambda _2^{}}{}}{\displaystyle }{\displaystyle \frac{dx^{}d^2\stackrel{}{k}_{}^{}}{\sqrt{x(1x)x^{}(1x^{})}}}R(x^{},\stackrel{}{k}_{}^{};\mathrm{\Lambda })\times `$
$`\times {\displaystyle \frac{4}{3}}{\displaystyle \frac{\overline{\alpha }(Q;\mathrm{\Lambda })}{Q^2}}\lambda _1,\lambda _2|S|\lambda _1^{},\lambda _2^{}x^{},\stackrel{}{k}_{}^{};\lambda _1^{},\lambda _2^{}|\psi .`$ (1)
Here, $`M^2`$ is the invariant-mass squared eigenvalue and $`x,\stackrel{}{k}_{};\lambda _1,\lambda _2|\psi `$ the associated eigenfunction. It is the probability amplitude for finding a $`q\overline{q}`$-Fock state in which the quark has longitudinal momentum fraction $`x`$ and transversal momentum $`\stackrel{}{k}_{}`$ and the anti-quark correspondingly $`1x`$ and $`\stackrel{}{k}_{}`$, and where the respective helicities are $`\lambda _1`$ and $`\lambda _2`$. The mean four-momentum transfers of the quarks and the spinor factor are respectively defined by

$`Q^2`$ $`=`$ $`{\displaystyle \frac{1}{2}}\left[(k_1k_1^{})^2+(k_2k_2^{})^2\right],`$ (2)
$`S=\lambda _1,\lambda _2|S|\lambda _1^{},\lambda _2^{}`$ $`=`$ $`\left[\overline{u}(k_1,\lambda _1)\gamma ^\mu u(k_1^{},\lambda _1^{})\right]\left[\overline{v}(k_2^{},\lambda _2^{})\gamma _\mu v(k_2,\lambda _2)\right].`$ (3)
The effective quark masses $`\overline{m}_{1,2}`$ and the effective coupling constant $`\overline{\alpha }(Q;\mathrm{\Lambda })`$ depend both, in general, on a regularization scale $`\mathrm{\Lambda }`$. The regulator function $`R(x^{},\stackrel{}{k}_{}^{};\mathrm{\Lambda })`$ restricts the range of integration and in general is a function of the same $`\mathrm{\Lambda }`$, see also below.

The current work is restricted to the lowest order of approximation (LOA) where $`\overline{m}=m`$ and $`\overline{\alpha }(Q;\mathrm{\Lambda })=\alpha `$. The expressions for the next-to-lowest order (NLO) can be found elsewhere.$`^\mathrm{?}`$ One has a fair confidence into the validity of Eq.(1), since the alternative method of Hamiltonian flow $`^\mathrm{?}`$ leads to the very same equation as in LOA.$`^\mathrm{?}`$ The same equation had also been obtained prior to that,$`^{\mathrm{?},\mathrm{?}}`$ with however less stringent arguments. The work of Wilson et al. $`^\mathrm{?}`$ had the same emphasis, but that it did not lead to the same formulas, see also Refs.$`^{\mathrm{?},\mathrm{?}}`$.

## 3 The crucial point in a simple model

Why is a regularization necessary at all?

In light-cone parametrization, the quark is at rest relative to the anti-quark when $`\stackrel{}{k}_{}=0`$ and $`x=\overline{x}\overline{m}_1/(\overline{m}_1+\overline{m}_2)`$. For very small deviations from these ‘equilibrium values’ the spinor factor is diagonal in the helicities, $`\lambda _1,\lambda _2|S|\lambda _1^{},\lambda _2^{}4\overline{m}_1\overline{m}_2\delta _{\lambda _1,\lambda _1^{}}\delta _{\lambda _2,\lambda _2^{}}`$, as can be veryfied from an explicit presentation of $`S`$.$`^\mathrm{?}`$ For very large deviations, particularly for $`\stackrel{}{k}_{}^{\mathrm{\hspace{0.17em}2}}\stackrel{}{k}_{}^{\mathrm{\hspace{0.17em}2}}`$, holds $`Q^2\stackrel{}{k}_{}^{\mathrm{\hspace{0.17em}2}}`$ and $`|S|2\stackrel{}{k}_{}^{\mathrm{\hspace{0.17em}2}}`$. The ratio is then a simple dimensionless number, $`S/Q^2=2`$, independent of $`\stackrel{}{k}_{}^{}`$. Both extremes are combined here by

$`{\displaystyle \frac{|S|}{Q}}^2={\displaystyle \frac{4\overline{m}_1\overline{m}_2}{Q^2}}+2,`$ (4)
which is considered as a model of the interaction in singlet states, dropping the less important spin-orbit interaction.

Unfortunately, I have not realized earlier $`^{\mathrm{?},\mathrm{?}}`$ that the innocent and finite number ‘2’ in Eq.(4) has the same orign as the familiar divergencies in gauge field theory. The latter arise, typically, when bilinar products of the elementatry Dirac interaction like in $`S`$ divided by some energy denominator like $`Q^2`$ are integrated over all phase space.

It was clear from the outset that the many-body Hamiltonian has to be regularized.$`^\mathrm{?}`$ Since fancy methods like dimensional regularization are not applicable, Fock-space regularization was considered to be sufficient.$`^\mathrm{?}`$ In practice, it has lead to difficulties and was was replaced by vertex regularization,$`^\mathrm{?}`$ where the elementary Dirac interaction at a vertex was endorsed with kind of a form factor $`F(\mathrm{\Lambda })`$, i.e.

$`\left[\overline{u}(1)\gamma ^\mu u(2)\right]ϵ_\mu (3)\left[\overline{u}(1)\gamma ^\mu u(2)\right]ϵ_\mu (3)F(k_1,k_2,k_3;\mathrm{\Lambda }).`$ (5)
Requiring that the off-shell mass of the two scattered particles $`M_0^2=(k_2+k_3)^2`$ is limited, $`F`$ becomes the step function $`F(k_1,k_2,k_3;\mathrm{\Lambda })=\mathrm{\Theta }(M_0^2\mathrm{\Lambda }^2)`$. In the absolute squares of the effective interaction, as in Eq.(1), it appears as a regulator function R as a consequence of regulating the theory from the outset.

## 4 Rewriting the integral equation in conventional momenta

Unpleasant is that $`x`$ and $`\stackrel{}{k}_{}`$ have different ranges $`(0x1,\mathrm{}k_x\mathrm{})`$. Instead of $`x`$ a $`k_z`$ $`(\mathrm{}k_z\mathrm{})`$ can be introduced by the transform $`^\mathrm{?}`$

$`x(k_z)`$ $`=`$ $`{\displaystyle \frac{E_1+k_z}{E_1+E_2}},\text{with }E_{1,2}=\sqrt{\overline{m}_{1,2}^{\mathrm{\hspace{0.17em}2}}+\stackrel{}{k}_{}^{\mathrm{\hspace{0.17em}2}}+k_z^2}.`$ (6)
The Jacobian of the transformation can be cast into the form

$`{\displaystyle \frac{dx}{x(1x)}}`$ $`=`$ $`{\displaystyle \frac{1}{A(k)}}{\displaystyle \frac{dk_z}{m_r}},\text{with }A(k)={\displaystyle \frac{1}{m_r}}{\displaystyle \frac{E_1E_2}{E_1+E_2}},`$ (7)
$`\text{and}{\displaystyle \frac{1}{m_r}}`$ $`=`$ $`{\displaystyle \frac{1}{\overline{m}_1}}+{\displaystyle \frac{1}{\overline{m}_2}},m_s=\overline{m}_1+\overline{m}_2.`$ (8)
In the same convention the kinetic energy becomes

$`T(k)`$ $`=`$ $`{\displaystyle \frac{\overline{m}_1^2+\stackrel{}{k}_{}^{\mathrm{\hspace{0.17em}2}}}{x}}+{\displaystyle \frac{\overline{m}_2^2+\stackrel{}{k}_{}^{\mathrm{\hspace{0.17em}2}}}{1x}}m_s^2C(k)\stackrel{}{k}^2,`$ (9)
$`\text{with}C(k)`$ $`=`$ $`(E_1+\overline{m}_1+E_2+\overline{m}_2)\left({\displaystyle \frac{1}{E_1+\overline{m}_1}}+{\displaystyle \frac{1}{E_2+\overline{m}_2}}\right),`$ (10)
without approximation. If one substitutes the wave function according to

$`\psi (x,\stackrel{}{k}_{})`$ $`=`$ $`\sqrt{{\displaystyle \frac{A(x,\stackrel{}{k}_{})}{x(1x)}}}\varphi (x,\stackrel{}{k}_{})`$ (11)
and drops explicit reference to the helicities, one arrives at an equation,

$`\left[M^2m_s^2C(k)\stackrel{}{k}^2\right]\varphi (\stackrel{}{k})={\displaystyle \frac{1}{4\pi ^2m_r}}{\displaystyle \frac{d^3\stackrel{}{k^{}}R}{\sqrt{A(\stackrel{}{k})A(\stackrel{}{k}^{})}}\frac{4}{3}\frac{\overline{\alpha }S}{Q^2}\varphi (\stackrel{}{k^{}})},`$ (12)
which is identical with Eq.(1), but which looks like one with usual 3-momenta.

## 5 Interpretation in configuration space

The main reason for introducing conventional 3-momenta is interpretation. It is more transparent in configuration space. Since the various factors $`A(\stackrel{}{k})`$ with their square-roots prevent straight-forward Fourier transforms, the non-relativistic approximation ($`\stackrel{}{k}^{\mathrm{\hspace{0.17em}2}}\overline{m}_{1,2}^2`$) is applied consistently. Using

$`A(k)=1,C(k)={\displaystyle \frac{m_s}{m_r}},Q^2=(\stackrel{}{k}\stackrel{}{k}^{})^2,`$ (13)
the model interaction of Eq.(4), and in addition the regulator $`R=1`$, Eq.(12) leads to a local Schrödinger equation

$`\left[M^2m_s^2{\displaystyle \frac{m_s}{m_r}}\stackrel{}{k}^2\right]\varphi (\stackrel{}{k})`$ $`=`$ $`{\displaystyle \frac{4\alpha }{3\pi ^2}}{\displaystyle d^3\stackrel{}{k^{}}\left(\frac{m_s}{Q^2}+\frac{1}{2m_r}\right)\varphi (\stackrel{}{k^{}})},`$ (14)
$`\left[M^2m_s^2{\displaystyle \frac{m_s}{m_r}}\stackrel{}{p}^{\mathrm{\hspace{0.17em}2}}\right]\psi (\stackrel{}{r})`$ $`=`$ $`2m_sV(r)\psi (\stackrel{}{r}),\text{ with }\stackrel{}{p}i\stackrel{}{}.`$ (15)
The potential $`V(r)`$ bears great similarity with $`V_{\text{hf-s}}(r)`$, the hyperfine interaction in the singlet channel found for hydrogen in all textbooks, i.e.

$`V(r)`$ $`=`$ $`{\displaystyle \frac{4}{3}}\alpha \left({\displaystyle \frac{1}{r}}+2{\displaystyle \frac{\pi }{m_rm_s}}\delta ^{(3)}(\stackrel{}{r})\right),`$ (16)
$`V_{\text{hf-s}}(r)`$ $`=`$ $`\alpha \left({\displaystyle \frac{1}{r}}+g_p{\displaystyle \frac{\pi }{m_em_p}}\delta ^{(3)}(\stackrel{}{r})\right).`$ (17)
The strange ‘2’ in Eq.(4) finds its explanation as the gyromagnetic ratio for a fermion, with $`g_p=2`$. But Eq.(16) has no solution! A Dirac-delta function is no proper function and must be regulated, for instance by a Yukawa-potential

$`V(r)`$ $`=`$ $`{\displaystyle \frac{4\alpha }{3}}\left({\displaystyle \frac{1}{r}}+{\displaystyle \frac{\mu ^2}{m_rm_s}}{\displaystyle \frac{e^{\mu r}}{r}}\right).`$ (18)
Important is that the delta ($`d^3\stackrel{}{r}\delta ^{(3)}(\stackrel{}{r})=1`$) and the Yukawa have the same strength $`d^3\stackrel{}{r}[\mu ^2\text{exp}(\mu r)/(2\pi r)]=1`$. Transforming back to momentum space gives

$`\left[M^2m_s^2{\displaystyle \frac{m_s}{m_r}}\stackrel{}{k}^2\right]\varphi (\stackrel{}{k})={\displaystyle \frac{4\alpha }{3\pi ^2}}{\displaystyle d^3\stackrel{}{k^{}}\left(\frac{m_s}{Q^2}+\frac{1}{2m_r}\frac{\mu ^2}{\mu ^2+Q^2}\right)\varphi (\stackrel{}{k^{}})}.`$ (19)
Obviously, replacing in configuration space the Dirac-delta function with a Yukawa potential corresponds to introducing in momentum space the regulator function $`R=\mu ^2/(\mu ^2+Q^2)`$.

The regularization of a Dirac-delta function is an old theme of nuclear physics in the context of pairing theory.$`^\mathrm{?}`$ It was the point of orign for the similarity transform,$`^{\mathrm{?},\mathrm{?}}`$ and was investigated recently,$`^\mathrm{?}`$ again.

## 6 Renormalization

The eigen values of the integral equation Eq.(19) depend now on a regularization scale $`\mu `$. In line with the current understanding of field theory one replaces $`\alpha `$ and $`m`$ by functions of $`\mu `$, such that every eigenvalue is stationary against small variations of $`\alpha `$, $`m`$ and $`\mu `$, i.e. $`dM_n^2/d\mu =0`$! The general procedure, however, is not possible here, since $`\alpha `$ and $`\mu `$ appear in Eq.(19) in the typical combination $`\alpha \mu ^2/(\mu ^2+Q^2)`$. One therefore proceeds by looking for a function $`\alpha _\mu `$ such, that the calculated mass of the pion, for example, agrees with the empirical value. The so obtained function $`\alpha _\mu `$ is considered universal. The actual value of $`\mu `$ can then be fixed by a second requirement.

## 7 The pion

For carrying out, in practice, the programme of Sec. 6 one needs an efficient tool for solving Eq.(19). Such one has been developed recently,$`^\mathrm{?}`$ restricted however for simplicity to spherically symmetric s-states. Fixing the up and the down mass to $`\overline{m}_u=\overline{m}_d=1.16`$ (the unit of mass is chosen here as 350 MeV$`/c^2`$), the calculated pion mass is required to agree with the experimental value $`^\mathrm{?}`$ to within eight digits. For every value of $`\mu `$ one obtains thus an $`\alpha _\mu `$ which is displayed in Fig. 3. The even greater surprise came when investigating the spectrum of the pion along the so obtained $`\alpha _\mu `$, as given in Fig. 3. The lowest state, the $`\pi ^+`$, stays nailed fixed to the empirical value, while the second and the third (as well as the higher ones) have an extremum at $`\mu 3.8`$. Such an extremum was not really expected, but in view of the renormalization group is useful: $`\mu `$ determines itsself from the solution!

For suffiently large values of $`\mu `$, say for $`\mu 10`$, see Fig. 3, the coupling constant decreases strongly and the spectrum becomes more and more the familiar Bohr spectrum with a small hyperfine shift. Obviously, it can be calculated perturbatively, indeed, for sufficiently small $`\alpha `$.

Having fixed now the regularization scale $`\mu \mu _0=3.8`$ gives the coupling constant $`\alpha \alpha _{\mu _0}=0.6904`$, see also Fig. 3. The wave function of the pion is plotted in Fig. 5. By a fit to an approximate expression $`\mathrm{\Phi }_a(p)=10/(1+p^2/p_a^2)`$, a width $`p_a=1.471`$ is obtained which is much larger than $`p_c=\frac{4}{3}\alpha m_r=0.5339`$, the Bohr momentum of the Coulomb wave function with the same $`\alpha `$. Having the wave function, one could, in principle, calculate the form factor and the distribution amplitude according to the exact expressions.$`^\mathrm{?}`$ This is however not a trivial undertaking, and, instead of, the above approximate expression was Fourier transformed to $`\psi (\stackrel{}{r})e^{p_ar}`$. The calculated root-mean-sqare radius of the pion becomes then

$$<r^2>^{\frac{1}{2}}=\frac{\sqrt{3}}{p_a}=0.663\text{ fm}.$$
(20)
The good agreement with the experimental value $`<r^2>_\pi ^{\frac{1}{2}}=0.657`$ fm$`^\mathrm{?}`$ is actually the result of fitting the quark masses $`\overline{m}_u=\overline{m}_u=406`$ MeV, see above. This exhausts all freedom in choosing the parameters of Eq.(19).

One should emphasize that the Yukawa potential in Eq.(19) at the scale $`\mu _0`$ pulls down essentially only one state. The others are left rather unperturbed at their Bohr values, see Fig. 3. The analogy with the pairing model in early nuclear physics is more than obvious.$`^\mathrm{?}`$ In a future and more rigorous solution of the full Eq.(12) one expects that the excited states can be disentangled into almost degenerate singlets and triplets, which in turn can be interpreted as an excitation of the pseudo-scalar pion, or the ground state of a vector meson, respectively. In any case, the first excited state of the simple model correlates very well with the mass of the $`\rho ^+`$ and the other vector mesons, see below.

## 8 On the question of confinement

The question of confinement is closely related to the potential $`V(r)`$, but the relation is subtle. One of the great advantages of light-cone quantization is the additivity of the free part and the interaction. Because of the dimensions of invariant mass squares the relation of potential and kinetic energy is somewhat hidden. In analogy to a classical Hamiltonian, the invariant mass-squared operator $`M^2`$ in Eq.(19) is interpreted as the square of a position and momentum dependent mass

$`M(r,p)=m_s\sqrt{1+{\displaystyle \frac{p^{\mathrm{\hspace{0.17em}2}}}{m_sm_r}}+{\displaystyle \frac{2}{m_s}}V(r)}.`$ (21)
For $`V(r)m_s`$ and $`p^{\mathrm{\hspace{0.17em}2}}m_sm_r`$ it could be expanded as

| $`M(r,p)`$ | $``$ | $`m_s`$ | + | $`{\displaystyle \frac{p^{\mathrm{\hspace{0.17em}2}}}{2m_r}}`$ | + | $`V(r)`$, |
| --- | --- | --- | --- | --- | --- | --- |
|  | $``$ | rest mass | + | kinetic energy | + | potential energy, |

These conditions, however, can not be satisfied everywhere. I therefore propose to introduce a relativistic potential energy by $`W(r)M(r,p=0)`$. This function is plotted in Fig. 5. It vanishes at $`r_0=0.5194`$ fm and the classical turning point is $`r_t=0.5300`$ fm, in agreement with Eq.(20). Since the sum of the quark masses is 812 MeV, the ionization threshold occurs at 542 MeV: In order to liberate the quarks in the pion, one has to invest more than three times the rest energy of a pion.

## 9 The meson masses

The remaining parameters of the theory, the masses of the strange, charm and bottom quark can then be determined by reproducing the masses of the pseudo-scalar mesons $`K,^{}`$ $`D^0`$ and $`B,^{}`$ respectively. This gives $`\overline{m}_s=508`$, $`\overline{m}_c=1666`$ and $`\overline{m}_b=5054\text{ MeV}`$. The remaining off-diagonal pseudo-scalar mesons are then calculated straightforwardly and compiled in Table 1. In view of the simplicity of the model, the agreement with the empirical values is remarkable, indeed, and at least as good as for any other model. The strong correlation of the first excited state with the vector mesons was mentioned.

## 10 Summary and some conclusions

The very difficult problem of solving the many-body Hamiltonian for QCD is replaced here by the problem of solving an effective QCD-inspired Hamiltonian. It is obtained from the QCD-Lagrangian in the light-cone gauge by the method of iterated resolvents or the Hamiltonian flow equations in the lowest non-trivial approximation. In order to avoid the numerical complexities of the full solution in light-cone coordinates, this effective interaction was stripped-off of almost all ingredients except the Coulomb and the hyperfine interaction, which are analyzed in a non-relativistic treatment with only 3-momenta. It is argued why the hyperfine interaction in the singlet channel needs to be regulated like the usual divergencies in gauge field theory.

It was courageous to apply such a simple model to the mystery particle of QCD, to the pion, but it turns out that both the pion’s mass and size are obtained without vacuum condensates of any kind, just by adjusting the canonical parameters of a gauge field theory, the coupling constant and the quark masses. The necessary regularization constant determines itself by the theory, in line with the current interpretation of the renormalization group. For the pion, as well as for the other mesons, one gets thus for the first time a QCD-inspired light-cone wave function by which one can compute the form factor by the available exact formulas, as well as the higher Fock space amplitudes.

The present approach exposes screening rather than confinement. The removal energy of a quark from a meson is higher than the pion’s mass. A bare quark is thus unlikely to be observed. One wonders whether this is not much more a physical picture than the strict linear confinement obtained by lattice gauge theory, the only available alternative approach for a non-perturbative description. But like the light-cone approach, the latter is burdened with its own pecularities among them the far extrapolation down to the pion.

In fact the present model runs short in several aspects. That the regulator function should apply to the whole kernel, and not only to one piece of the interaction, is a technical detail, which can be easily corrected in future work. More importent is whether the two-gluon annihilation interaction, which was omitted here on perpose, can account for the flavor diagonal mesons and the so important aspects of isospin.

Astounding is also that the present model for QCD differs from QED only by the color factor $`\frac{4}{3}`$ in the coupling constant. Can it be true that the essential difference between these two theories with their so distinctly different phenomenology is manifest only as large and small coupling?

Depite all of that I conclude that the light-cone approach to hadronic physics may now have a fair chance to compute the hadronic spectra and to predict the hadronic wave functions in line with a covariant theory.

## References