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# 1 Introduction

## 1 Introduction

The Hera collider enables the study of deep inelastic neutral current scattering $`epeX`$ at very high squared momentum transfers $`Q^2`$, thus probing the structure of $`eq`$ interactions at very short distances. At large scales new phenomena not directly detectable may become observable as deviations from the Standard Model predictions. A convenient tool to assess the experimental sensitivity beyond the maximal available center of mass energy and to parameterise indirect signatures of new physics is the concept of four-fermion contact interactions. Possible sources of such contact terms are either a substructure of the fermions involved or the exchange of a new heavy particle. In the first case a compositeness scale can be related to the size of the composite object, while in the second case the scale parameter is related to the mass and coupling of the exchanged boson.

The principle idea of this contact interaction analysis at Hera is to fix the Standard Model and its parameters, in particular the parton distributions, using experimental data at low $`Q^2`$, where the theory is well established, and to extrapolate the prediction towards high momentum transfers, where deviations due to new physics are expected to be most prominent. In the present paper the differential cross section $`\mathrm{d}\sigma /\mathrm{d}Q^2`$ is analysed over a $`Q^2`$ range of $`20030,000\mathrm{GeV}^2`$ and possible deviations from the Standard Model prediction are searched for in the framework of $`(\overline{e}e)(\overline{q}q)`$ contact interactions. The data are interpreted within conventional scenarios such as model independent compositeness scales of various chiral structures, a classical quark form factor approach and the exchange of heavy leptoquarks. Another investigation concerns the search for low scale quantum gravity effects, which may be observable at Hera via the exchange of gravitons coupling to Standard Model particles and propagating into extra spatial dimensions.

## 2 Data Analysis

The contact interaction analysis is based on the recent $`e^+p`$ neutral current cross section measurements by the H1 experiment discussed in detail in ref. . The data have been collected at a center of mass energy of $`\sqrt{s}=300\mathrm{GeV}`$ and correspond to an integrated luminosity of $`=35.6\mathrm{pb}^1`$, representing a tenfold increase over a previous analysis . The cross section $`\mathrm{d}\sigma /\mathrm{d}Q^2`$ is determined from a purely inclusive measurement of the final state positron with energy $`E_e^{}`$ and polar angle $`\theta _e`$ (defined with respect to the proton direction). The squared momentum transfer is calculated via $`Q^2=4E_eE_e^{}\mathrm{cos}^2(\theta _e/2)`$, where $`E_e`$ is the lepton beam energy. The data are corrected for detector effects and QED radiation and represent the cross section within the kinematic phase space of momentum transfer $`Q^2200\mathrm{GeV}^2`$ and inelasticity $`y=1E_e^{}/E_e\mathrm{sin}^2(\theta _e/2)<0.9`$. The dominant experimental systematics are the uncertainties of the reconstructed positron energy scale, varying between $`0.7\%`$ and $`3\%`$ depending on the detector region, and of the scattering angle, known to $`13`$ mrad. An overall normalisation uncertainty of $`1.5\%`$ is due to the luminosity determination. The differential cross section is shown in figure 1.

The double differential cross section is given in the Standard Model by

$`{\displaystyle \frac{\mathrm{d}^2\sigma (e^+pe^+X)}{\mathrm{d}x\mathrm{d}Q^2}}`$ $`=`$ $`{\displaystyle \frac{2\pi \alpha ^2}{xQ^4}}\left\{Y_+F_2(x,Q^2)Y_{}xF_3(x,Q^2)y^2F_L(x,Q^2)\right\},`$ (1)
where $`x=Q^2/ys`$ is the Bjorken scaling variable and $`Y_\pm =1\pm (1y)^2`$. The generalised proton structure functions $`F_2(x,Q^2)`$, $`F_3(x,Q^2)`$ and $`F_L(x,Q^2)`$ are related to the parton densities and the quark-$`\gamma `$ and quark-$`Z`$ couplings. The cross section calculations are done in the DIS scheme in next-to-leading-order using as standard the CTEQ5D parton parameterisation . Integrating eq. (1) over $`x`$ gives the $`Q^2`$ spectrum which describes the data very well over six orders of magnitude, see figure 1.

In order to derive quantitative tests of the Standard Model and to search for new physics hypotheses, a $`\chi ^2`$ analysis of the data is performed taking the dominant error sources and uncertainties into account. The $`\chi ^2`$ function is defined as

$`\chi ^2`$ $`=`$ $`{\displaystyle \underset{i}{}}\left({\displaystyle \frac{\widehat{\sigma }_i^{exp}f_n\widehat{\sigma }_i^{th}(1_k\mathrm{\Delta }_{ik}(\epsilon _k))}{\mathrm{\Delta }\widehat{\sigma }_i^{exp}f_n}}\right)^2+\left({\displaystyle \frac{f_n1}{\mathrm{\Delta }f_n}}\right)^2+{\displaystyle \underset{k}{}}\epsilon _k^2.`$ (2)
Here $`\widehat{\sigma }_i`$ denotes the experimental or theoretical cross section in the $`Q^2`$ bin $`i`$ and $`f_n`$ is the overall normalisation parameter with an uncertainty $`\mathrm{\Delta }f_n=0.015`$. The experimental error $`\mathrm{\Delta }\widehat{\sigma }_i^{exp}`$ includes statistical and uncorrelated systematic errors added in quadrature. The functions $`\mathrm{\Delta }_{ik}(\epsilon _k)`$ describe for the $`i^{th}`$ bin effects due to correlated systematic errors associated to different sources $`k`$. They depend quadratically on the fit parameters $`\epsilon _k`$, which may be interpreted as pulls, i.e. shifts caused by systematics normalised to their error estimates. There are three sources of correlated systematic errors taken into account: the experimental uncertainties of the positron energy scale and the scattering angle and the uncertainty of the strong coupling entering in the Standard Model prediction (see below).

Concerning cross section calculations the major uncertainty comes from the parton distributions, which are generally provided without error estimates. Different parametrisations in the DIS scheme, MRST 99  and GRV 94  in addition to CTEQ5D, are used to estimate the uncertainties due to various models and assumptions. They do not differ in the shape of the $`Q^2`$ spectrum significantly, but rather in the absolute cross section prediction by up to 2.8%, e.g. comparing CTEQ5D with MRST 99. Several other MRST sets are used for cross checks, like those with different admixtures of quarks and gluons at high $`x`$, or different treatments of strange and charm quarks. All these MRST variants essentially change the overall normalisation of the cross section prediction by less than $`1\%`$, being well below the measurement errors, and introduce no relevant additional $`Q^2`$ dependence. The largest uncertainty comes from the strong coupling constant. Using parton distributions evaluated for couplings differing from the central value of $`\alpha _s(M_Z)=0.118`$ by $`\pm 0.005`$ cause variations of the cross section by $`\pm 1\%`$ at low $`Q^2`$ and up to $`4\%`$ at high $`Q^2`$. These shifts are parameterised and taken into account as correlated systematic error in the $`\chi ^2`$ fit of eq. (2). It should be noted that the applied parton density functions have not been constrained by high $`Q^2`$ data from the Hera experiments. A comparison with a recent QCD analysis in the $`\overline{\text{MS}}`$ scheme , which attempts to provide parton distributions including errors, confirms that the above choice of various parton density functions is a reasonable representation of systematic uncertainties.

A fit of the cross section $`\mathrm{d}\sigma /\mathrm{d}Q^2`$ to the Standard Model expectation using CTEQ5D parton densities yields $`\chi ^2/\mathrm{dof}=12.3/16`$ with a normalisation parameter $`f_n=1.004`$. Limits of a model parameter are derived by varying the parameter until the $`\chi ^2`$ value changes by a certain amount with respect to the Standard Model fit, e.g. $`\chi ^2\chi _{SM}^2=3.84`$ for 95% confidence level (CL). Systematics due to different parton distributions are taken into account by always quoting the most conservative result of the various fits, i.e. the smallest value in case of a lower limit.

## 3 Contact Interaction Phenomenology

New currents or heavy bosons may produce indirect effects through the exchange of a virtual particle interfering with the $`\gamma `$ and $`Z`$ fields of the Standard Model. For particle masses and scales well above the available energy, $`\mathrm{\Lambda }\sqrt{s}`$, such indirect signatures may be investigated by searching for a four-fermion pointlike $`(\overline{e}e)(\overline{q}q)`$ contact interaction. The most general chiral invariant Lagrangian for neutral current vector-like contact interactions can be written in the form

$`_V`$ $`=`$ $`{\displaystyle \underset{q=u,d}{}}\{\eta _{LL}^q(\overline{e}_L\gamma _\mu e_L)(\overline{q}_L\gamma ^\mu q_L)+\eta _{LR}^q(\overline{e}_L\gamma _\mu e_L)(\overline{q}_R\gamma ^\mu q_R)`$ (3)
$`+\eta _{RL}^q(\overline{e}_R\gamma _\mu e_R)(\overline{q}_L\gamma ^\mu q_L)+\eta _{RR}^q(\overline{e}_R\gamma _\mu e_R)(\overline{q}_R\gamma ^\mu q_R)\},`$
where the indices $`L`$ and $`R`$ denote the left-handed and right-handed fermion helicities and the sum extends over up-type and down-type quarks and antiquarks $`q`$. In deep inelastic scattering at high $`Q^2`$ the contributions from the first generation $`u`$ and $`d`$ quarks completely dominate and contact terms arising from sea quarks $`s`$, $`c`$ and $`b`$ are strongly suppressed. Thus, there are eight independent effective coupling coefficients, four for each quark flavour

$`\eta _{ab}^q`$ $``$ $`ϵ{\displaystyle \frac{g^2}{\mathrm{\Lambda }_{ab}^{q2}}},`$ (4)
where $`a`$ and $`b`$ indicate the $`L,R`$ helicities, $`g`$ is the overall coupling strength, $`\mathrm{\Lambda }_{ab}^q`$ is a scale parameter and $`ϵ`$ is a prefactor, often set to $`ϵ=\pm 1`$, which determines the interference sign with the Standard Model currents. The ansatz eq. (3) can be easily applied to any new phenomenon, e.g. $`(eq)`$ compositeness, leptoquarks or new gauge bosons, by an appropriate choice of the coefficients $`\eta _{ab}`$. Scalar and tensor interactions of dimension 6 operators involving helicity flip couplings are strongly suppressed at Hera  and therefore not considered.

It has been recently suggested that gravitational effects may become strong at subatomic distances and thus measurable in collider experiments . In such a scenario, which may be realised in string theory, gravity is characterised by a scale $`M_S𝒪(\mathrm{TeV})`$ in $`4+n`$ dimensions. The extra spatial dimensions $`n`$ are restricted to a volume associated with the size $`R`$ and the scales in $`4+n`$ and the ordinary $`4`$ dimensions are related by

$`M_P^2`$ $``$ $`R^nM_S^{2+n},`$ (5)
where $`M_P10^{19}\mathrm{GeV}`$ is the Planck mass. An exciting consequence would be a modification of Newton’s law at distances $`r<R`$, where the gravitational force would rise rapidly as $`F1/r^{2+n}`$ and become strong at the scale $`M_S`$. Experimentally, gravity is essentially not tested in the sub-millimeter range  and scenarios with $`n>2`$ extra dimensions at large distances $`R100\mu `$m are conceivable.

In the phenomenology of  the Standard Model particles are confined to 4 dimensions while only the graviton propagates as massless spin 2 particle into the $`n`$ extra dimensions. When projected onto the normal 4 dimensional space the graviton appears as a spectrum of Kaluza-Klein excitations with masses $`m^{(j)}=j/R`$, including the zero-mass state. The graviton fields $`G_{\mu \nu }^{(j)}`$ couple to the Standard Model particles via the energy-momentum tensor $`T_{\mu \nu }`$

$`_G`$ $`=`$ $`{\displaystyle \frac{\sqrt{8\pi }}{M_P}}G_{\mu \nu }^{(j)}T^{\mu \nu }.`$ (6)
Summation over the whole tower of Kaluza-Klein states $`j`$ with masses up to the scale $`M_S`$ compensates the huge $`1/M_P`$ suppression and results in an effective contact interaction coupling

$`\eta _G`$ $`=`$ $`{\displaystyle \frac{\lambda }{M_S^4}},`$ (7)
where $`\lambda `$ is the coupling strength of order unity. Note that the scale dependence of gravitational effects is very different from that of conventional contact interactions, eq. (4). In deep inelastic scattering graviton exchange may contribute to the electron-quark subprocess, but the new interaction also induces electron-gluon scattering which is not present in the Standard Model.

It is worth recalling that contact interactions as an effective theory can only be formulated in lowest order. They contribute  to the structure functions $`F_2(x,Q^2)`$ and $`xF_3(x,Q^2)`$, but are absent in $`F_L(x,Q^2)`$. On the other hand a cross section calculation in next-to-leading-order QCD appears to be more reliable. This conceptual limitation is less important in the DIS renormalisation scheme, where the expression for the dominant structure function $`F_2`$ is identical and $`xF_3`$ receives only minor corrections in second order.

Contact interaction phenomena are best observed as a modification of the expected $`Q^2`$ dependence and all information is essentially contained in the differential cross section $`\mathrm{d}\sigma /\mathrm{d}Q^2`$, analysed in the present paper. Calculations using the Standard Model prediction, eq. (1), show that for the scenarios under study only those models involving both $`u`$ and $`d`$ quarks with pure $`LL`$ or $`RR`$ couplings and negative interference are slightly more sensitive to an analysis in two variables $`Q^2`$ and $`x`$. With the present luminosity the gain in setting limits on the respective scales would be $`20\%`$ for the negatively interfering $`LL`$ and $`RR`$ composite models and $`10\%`$ for the leptoquark $`S_1^L`$. For all other scenarios the differences are marginal.

## 4 Compositeness Scales

In the Standard Model the fundamental particles – leptons, quarks and gauge bosons – are assumed to be pointlike. A possible fermion compositeness or substructure can be expressed through the $`\eta `$ coefficients of eq. (4) which depend only on the ratio of the coupling constant over the scale. In the present analysis the interference sign is set to $`ϵ=\pm 1`$ for the chiral structures under study, the coupling strength $`g`$ is by convention chosen as $`g^2=4\pi `$ and the compositeness scale $`\mathrm{\Lambda }`$ is assumed to be the same for all up-type and down-type quarks. Among the many possible combinations the following models are investigated: (i) the pure chiral couplings $`LL`$, $`LR`$, $`RL`$ and $`RR`$, (ii) the vectorial couplings $`VV`$, $`AA`$ and $`VA`$, (iii) the mixtures $`LL+RR`$ and $`LR+RL`$.

It is appropriate to analyse the differential cross section in terms of the coupling coefficients $`\eta =ϵ\mathrm{\hspace{0.17em}4}\pi /\mathrm{\Lambda }^2`$. Figure 2 shows the values of $`\chi ^2`$ as a function of $`ϵ/\mathrm{\Lambda }^2`$ from fits to the models under study. In general one observes that the distributions become narrower, i.e. the sensitivity increases, the more chiral structures are involved. The pure chiral couplings prefer negative values of $`\eta `$. This is a consequence of the trend of the data $`(\mathrm{d}\sigma /\mathrm{d}Q^2)/(\mathrm{d}\sigma ^{SM}/\mathrm{d}Q^2)`$ to be slightly low around $`Q^24,00012,000\mathrm{GeV}^2`$ and being followed by an upward fluctuation at higher $`Q^2`$ (see figure 1), which favour a negative interference term. Note that the $`LL`$ and $`RR`$ models and the $`LR`$ and $`RL`$ models are almost indistinguishable in deep inelastic unpolarised $`e^+p`$ scattering. Within each couple the exchanged quantum numbers are the same and therefore the combinations $`LL+RR`$ and $`LR+RL`$ are investigated as well. The data are more sensitive to the $`VV`$, $`AA`$ and $`VA`$ models, where all chiral structures contribute. The most restrictive range of $`ϵ/\mathrm{\Lambda }^2`$ is obtained for the $`VV`$ model, where all contact terms enter with the same sign. Figure 2 also shows that different parton distributions have little influence on the results.

The results of the $`\chi ^2`$ fits are shown in figure 3 and compiled in table 1. Within two standard deviations the couplings $`ϵ/\mathrm{\Lambda }^2`$ are compatible with the Standard Model for all parton density functions used.

Limits on the compositeness scale parameters $`\mathrm{\Lambda }^+`$ and $`\mathrm{\Lambda }^{}`$, corresponding to positive and negative interference, are quoted in table 1 and also presented in figure 3. They vary between $`1.3\mathrm{TeV}`$ and $`5.5\mathrm{TeV}`$ depending on the chiral structure of the model and are in most cases asymmetric with respect to the interference sign. In general the values of $`\mathrm{\Lambda }^+`$ are more restrictive due to the downward trend of the data at intermediate $`Q^2`$ prefering models with negative interference. As an illustration of the sensitivity of the data to compositeness scales figure 4 shows the 95% CL contributions of $`\mathrm{\Lambda }^\pm `$ for the $`VV`$ model using CTEQ5D parton densities.

The results of direct searches for $`(eq)`$ compositeness are compatible with those of other experiments at Hera, Lep and Tevatron. To date the most stringent limits come from $`e^+e^{}`$ experiments  with typical cut-off values of $`310\mathrm{TeV}`$ assuming, however, in general the same scale parameter $`\mathrm{\Lambda }`$ for all five active quarks. The Zeus collaboration  investigates only models in which at least 2 couplings contribute and derives limits between $`1.7\mathrm{TeV}`$ and $`5\mathrm{TeV}`$ relying solely on the shape of measured distributions. The $`p\overline{p}`$ experiments  measure Drell-Yan production and quote limits on $`\mathrm{\Lambda }`$ between $`2.5\mathrm{TeV}`$ and $`6\mathrm{TeV}`$, where the normalisation is based on the number of observed $`Z`$ bosons. Model dependent indirect limits of order $`10\mathrm{TeV}`$ for the pure chiral couplings involving $`u`$ and $`d`$ quarks can be set by atomic parity violation experiments .

## 5 Form Factors

An alternative method to study possible fermion substructures is to assign a finite size of radius $`R`$ to the electroweak charges of leptons and/or quarks while treating the gauge bosons $`\gamma `$ and $`Z`$ still as pointlike particles . A convenient parametrisation is to introduce ‘classical’ form factors $`f(Q^2)`$ at the gauge boson–fermion vertices, which are expected to diminish the Standard Model cross section at high momentum transfer

$`f(Q^2)`$ $`=`$ $`1{\displaystyle \frac{1}{6}}r^2Q^2,`$ (8)
$`{\displaystyle \frac{d\sigma }{dQ^2}}`$ $`=`$ $`{\displaystyle \frac{d\sigma ^{SM}}{dQ^2}}f_e^2(Q^2)f_q^2(Q^2).`$ (9)
The root of the mean-square radius of the electroweak charge distribution, $`R=\sqrt{r^2}`$, is taken as a measure of the particle size. The data are analysed in terms of a single form factor $`f_q`$, i.e. only the quarks are allowed to be extended objects while the positron has no structure by setting $`f_e1`$. This assumption is justified, since the pointlike nature of the electron/positron is already established down to extremely low distances in $`e^+e^{}`$ and $`(g2)_e`$ experiments . The analysis yields an upper limit at 95% CL of the light quark radius of

$`R_q`$ $`<`$ $`1.710^{16}\mathrm{cm}.`$
The result is compatible with those from other measurements. In an analysis of Drell-Yan production of $`e^+e^{}`$ and $`\mu ^+\mu ^{}`$ pairs in $`p\overline{p}`$ scattering the CDF collaboration  finds a quark size of $`R_q<110^{16}\mathrm{cm}`$ assuming pointlike leptons. A complementary analysis of the contributions of anomalous magnetic dipole moments to the $`Zq\overline{q}`$ vertex using hadronic $`Z`$ decays gives $`R_q<1.210^{16}\mathrm{cm}`$ for the light $`u`$ and $`d`$ quarks .

## 6 Leptoquarks

Leptoquarks are colour triplet bosons of spin 0 or 1, carrying lepton ($`L`$) and baryon ($`B`$) number and fractional electric charge. They couple to lepton–quark pairs and appear in extensions of the Standard Model which try to establish a connection between leptons and quarks. Leptons and quarks may be arranged in common multiplets, like in Grand Unified Theories or superstring motivated $`E_6`$ models, or they may have a common substructure as in composite models. A fermion number $`F=L+3B`$ is defined, which takes the values $`F=2`$ for leptoquarks coupling to $`e^{}q`$ and $`F=0`$ for leptoquarks coupling to $`e^{}\overline{q}`$. For positrons the fermion number $`F`$ changes by two. The leptoquark mass $`M_{LQ}`$ and its coupling $`\lambda `$ are related to the contact interaction coefficients of eq. (4) via $`g/\mathrm{\Lambda }=\lambda /M_{LQ}`$. The notation and the coupling coefficients $`\eta _{ab}`$ for leptoquarks <sup>1</sup><sup>1</sup>1The coupling coefficients are taken from ref.  with the signs corrected (i.e. reversed) for $`F=2`$ scalar and $`F=0`$ vector leptoquarks according to ref. . are given in table 2. The only unknown parameter is the ratio $`M_{LQ}/\lambda `$. Note that the vector leptoquarks have coupling coefficients twice as large in magnitude compared to scalar leptoquarks.

The differential cross section analysis gives no evidence for a virtual leptoquark signal. The resulting lower limits on $`M_{LQ}/\lambda `$ are summarised in table 2 including the full error propagation and a variation of parton densities. In general leptoquarks with positive interference provide stronger limits compared to those with negative interference. This observation is consistent with the results found for compositeness models. The vector leptoquarks which couple to $`u`$ quarks provide the most restrictive limits of $`M_{LQ}/\lambda 𝒪(1\mathrm{TeV})`$. It should be emphasised that upper bounds on the coupling strength $`\lambda `$ can only be set for leptoquark masses exceeding the accessible center of mass energy of Hera. Masses far above 300 GeV are excluded for almost all types of leptoquarks with a coupling of $`\lambda 1`$.

These measurements are a considerable improvement over the previous analysis . But it should be noted that changes  in the signs of couplings $`\eta _{ab}^q`$ reduce the sensitivity for $`F=2`$ vector leptoquarks and lead e.g. to weaker limits for $`\stackrel{~}{V}_0^R`$ and $`V_1^L`$ despite the increased luminosity. As an example of the sensitivity of the data to virtual leptoquark exchange figure 5 shows the contributions given by the lower limits on $`M_{LQ}/\lambda `$ for the scalar leptoquark $`S_{1/2}^R`$ and the vector leptoquark $`V_{1/2}^R`$. Both leptoquarks have $`RL`$ couplings to up and down quarks, which differ in magnitude and interference sign.

The present contact interaction results complement the direct leptoquark searches of the H1 collaboration , which have recently been extended beyond the kinematic reach of Hera up to masses of $`M_{LQ}400\mathrm{GeV}`$. The coupling limits derived in both analyses are compatible with each other in the mass region where they overlap. Virtual leptoquark exchange has also been studied in $`e^+e^{}`$ annihilation experiments at Lep . Typical limits on $`M_{LQ}/\lambda `$ are in the range $`0.31.8\mathrm{TeV}`$, but the sensitivity to particular leptoquark types is different from deep inelastic $`e^+p`$ scattering. In most cases the Lep results provide more stringent bounds; the limits for $`S_0^R`$, $`\stackrel{~}{S}_{1/2}^L`$ and $`V_0^R`$ are comparable and those of $`V_{1/2}^R`$ and $`\stackrel{~}{V}_{1/2}^L`$ are superior at Hera.

## 7 Large Extra Dimensions

The contributions of virtual graviton exchange to deep inelastic scattering have been derived from the cross sections given in ref.  for $`e^+e^{}`$ collisions by applying crossing relations. The basic processes of elastic $`e^+qe^+q`$ and $`e^+ge^+g`$ scattering can be written as <sup>2</sup><sup>2</sup>2 The following formulae of ref.  are used: eq. (79) for the $`eq`$ contributions, eq. (77) for the $`eg`$ contribution replacing the photons by gluons, and eqs. (A.5), (A.7) – (A.9) to expand the functions $`G_i(s/t)`$. The present $`eq`$ results are in agreement with , but the $`eg`$ part differs by a factor of $`1/4`$. The cross section formulae of refs.  and  cannot be confirmed and the results of both publications are inconsistent with each other.

$`{\displaystyle \frac{\mathrm{d}\sigma (e^+qe^+q)}{\mathrm{d}t}}`$ $`=`$ $`{\displaystyle \frac{\mathrm{d}\sigma ^{SM}}{\mathrm{d}t}}+{\displaystyle \frac{\mathrm{d}\sigma ^G}{\mathrm{d}t}}+{\displaystyle \frac{\mathrm{d}\sigma ^{\gamma G}}{\mathrm{d}t}}+{\displaystyle \frac{\mathrm{d}\sigma ^{ZG}}{\mathrm{d}t}},`$ (10)
$`{\displaystyle \frac{\mathrm{d}\sigma ^G}{\mathrm{d}t}}`$ $`=`$ $`{\displaystyle \frac{\pi \lambda ^2}{32M_S^8}}{\displaystyle \frac{1}{s^2}}\left\{32u^4+64u^3t+42u^2t^2+10ut^3+t^4\right\},`$ (11)
$`{\displaystyle \frac{\mathrm{d}\sigma ^{\gamma G}}{\mathrm{d}t}}`$ $`=`$ $`{\displaystyle \frac{\pi \lambda }{2M_S^4}}{\displaystyle \frac{\alpha e_q}{s^2}}{\displaystyle \frac{(2u+t)^3}{t}},`$ (12)
$`{\displaystyle \frac{\mathrm{d}\sigma ^{ZG}}{\mathrm{d}t}}`$ $`=`$ $`{\displaystyle \frac{\pi \lambda }{2M_S^4}}{\displaystyle \frac{\alpha }{s^2\mathrm{sin}^22\theta _W}}\left\{v_ev_q{\displaystyle \frac{(2u+t)^3}{tm_Z^2}}a_ea_q{\displaystyle \frac{t(6u^2+6ut+t^2)}{tm_Z^2}}\right\},`$ (13)
$`{\displaystyle \frac{\mathrm{d}\sigma (e^+ge^+g)}{\mathrm{d}t}}`$ $`=`$ $`{\displaystyle \frac{\pi \lambda ^2}{8M_S^8}}{\displaystyle \frac{u}{s^2}}\left\{2u^3+4u^2t+3ut^2+t^3\right\}`$ (14)
in an obvious notation of Standard Model (SM), pure graviton (G), $`\gamma G`$ and $`ZG`$ interference contributions. Here $`s`$, $`t=Q^2`$ and $`u`$ are the Mandelstam variables, $`e_q`$ is the quark charge and $`v_f`$ and $`a_f`$ are the vector and axial vector couplings of the fermions to the $`Z`$. The corresponding cross sections for $`e^+\overline{q}`$ scattering are obtained by replacing $`e_qe_q`$ and $`v_qv_q`$ in the expressions above. In order to get the inclusive $`e^+p`$ cross section the subprocesses have to be integrated over the $`x`$ dependent parton distributions, $`q(x)`$, $`\overline{q}(x)`$ and $`g(x)`$, and to be summed up

$`{\displaystyle \frac{\mathrm{d}\sigma (e^+pe^+X)}{\mathrm{d}Q^2}}`$ $`=`$ $`{\displaystyle dx\left\{q(x)\frac{\mathrm{d}\sigma (e^+q)}{\mathrm{d}t}+\overline{q}(x)\frac{\mathrm{d}\sigma (e^+\overline{q})}{\mathrm{d}t}+g(x)\frac{\mathrm{d}\sigma (e^+g)}{\mathrm{d}t}\right\}}.`$ (15)
Note, that expected gravitational effects arising from the gluon contribution are for the highest $`Q^2`$ values of the order percent compared to those coming from the quarks and antiquarks.

The strength of virtual graviton exchange to the cross section contributions is characterised by the ratio $`\lambda /M_S^4`$. The coupling $`\lambda `$ depends on the full theory and is expected to be of order unity. Also the sign of interference with the Standard Model particles is a priori not known. Therefore the coupling is set to $`\lambda =\pm 1`$, following the convention of . The data analysis is similar to the procedures described above. Gravitational effects are searched for by fitting the differential cross section to the above formulae with $`\lambda /M_S^4`$ treated as free parameter. The result of $`\lambda /M_S^4=3.3{}_{3.3}{}^{+4.2}{}_{1.3}{}^{+0.4}\mathrm{TeV}_{}^{4}`$, where the second error reflects the parton density variation, is compatible with the Standard Model expectation. Lower limits at 95% CL on $`M_S`$ for positive and negative coupling are then derived from the change in $`\chi ^2`$ with respect to the Standard Model fit, yielding

$`M_S>0.48\mathrm{TeV}`$ $`\mathrm{for}\lambda =+1,`$
$`M_S>0.72\mathrm{TeV}`$ $`\mathrm{for}\lambda =1.`$
Possible effects of graviton exchange to the data, as given by the exclusion limits, are illustrated in figure 6.

Similar investigations of virtual graviton effects in $`e^+e^{}`$ annihilation into fermion and boson pairs provide comparable limits . From the corresponding reaction of quark pair production scales of $`M_S`$ lower than $`0.50.65\mathrm{TeV}`$ can be excluded. Combining all reactions that lead to two-fermion final states limits approaching $`1\mathrm{TeV}`$ can be set.

## 8 Conclusions

Neutral current deep inelastic cross section measurements are analysed to search for new phenomena mediated through $`(\overline{e}e)(\overline{q}q)`$ contact interactions. No significant signal for compositeness, a quark form factor and virtual leptoquark or graviton exchange is found and the data are used to set limits which supersede and substantially improve former H1 results .

Limits on $`(eq)`$ compositeness are derived within a model independent analysis for scenarios involving one or more chiral couplings. The lower bounds on the scale parameters $`\mathrm{\Lambda }^\pm `$ range between $`1.3\mathrm{TeV}`$ and $`5.5\mathrm{TeV}`$ for a coupling strength $`g=\sqrt{4\pi }`$, depending on the chiral structure of the model.

A different approach to substructures is the concept of form factors. Such an analysis yields an upper limit of the size of the light $`up`$ and $`down`$ quarks of $`R_q<1.710^{16}\mathrm{cm}`$ assuming a pointlike lepton.

A study of virtual leptoquark exchange yields lower limits on the ratio $`M_{LQ}/\lambda `$ which for all types (except one) exceed the collider center of mass energy and approach $`1\mathrm{TeV}`$ for vector leptoquarks with couplings to up quarks. These measurements complement and extend the direct leptoquark searches at Hera to high masses $`M_{LQ}>\sqrt{s}`$.

In a search for possible effects of low scale quantum gravity with gravitons coupling to Standard Model particles and propagating into extra spatial dimensions, lower limits on the effective Planck scale $`M_S`$ of $`0.48\mathrm{TeV}`$ and $`0.72\mathrm{TeV}`$ for positive and negative coupling, respectively, are found.

Acknowledgements. We are grateful to the Hera machine group whose outstanding efforts have made and continue to make this experiment possible. We thank the engineers and technicians for their work in constructing and now maintaining the H1 detector, our funding agencies for financial support, the Desy technical staff for continual assistance, and the Desy directorate for the hospitality extended to the non–Desy members of the collaboration. We gratefully acknowledge valuable discussions with G.F. Giudice.


text:
# Flexible Linear Polyelectrolytes in Multivalent Salt Solutions: Solubility Conditions

## I Introduction

The precipitation and dissolution of linear polyelectrolytes with the addition of multivalent salt or particles have been extensively studied . In DNA the precipitation provides a promising mechanism to ”pack” long DNA, a critical problem in gene therapy. Moreover, it is correlated with highly accelerated rates of DNA renaturation and cyclisation. Therefore, it is important to determine the concentration of multivalent salt or particles at which the precipitated DNA dissolves in the solution. Furthermore, it is crucial to determine the effective charge of the DNA in the precipitated and dissolved states to determine their interaction with cells.

It has been shown experimentally that the transitions are nearly independent of the details of the linear polyelectrolyte (such as charge density, degree of flexibility, molecular weight, structure function, etc.). That is, flexible (single stranded DNA and Polystyrene Sulphonate) and semiflexible chains (double stranded DNA) can be described by the same thermodynamic model even though flexible chains collapse into amorphous dense spheres and long semiflexible chains into toroid conformations .

We recently develop a thermodynamic model that explains the universal nature of the multivalent counterion induced precipitation transition in low concentration of monovalent salts. In this paper we analyze the redissolution transition by extending our two state model to include large concentrations of multivalent salt.

The experimental diagrams of the logarithm of concentration of monomers $`\varphi `$ versus the logarithm of the concentration of multivalent salt $`m`$ have three regions (A, B and C) separated by 2 transitions lines (L1-L2 and L3) , shown schematically in Fig. 1. Region A corresponds to polyelectrolytes dissolved in water with expanded-stretched conformation at low $`m`$ values. Region B at intermediate multivalent salt concentrations $`m`$ is a solution of collapsed polyelectrolytes (sometimes considered as a coexistence of two phases: one rich and one poor in polyelectrolytes). Region C at large $`m`$ values contains polymers dissolved in water in expanded-coiled conformations. The transition line between the A and B regions, L2, at low monovalent salt concentrations is linear with a slope comparable to $`1/z`$, where $`z`$ is the valence of the counterions of the added salt. In the presence of monovalent salt there is a nearly horizontal transition line, L1, at very low concentrations of monomers. The transition line between regions B and C is horizontal (i.e., independent of the concentration of monomers) in the full regime. In our previous paper  we discussed the transition between regions A and B and explained the transition in the regime L2 as the creation of collapsed conformations of polymers whose charge is compensated by condensed multivalent salt. Our model also predicts the transition L1 in the presence of large amounts of monovalent salt. In this paper we study the transition between the regions B and C in solutions with very low (negligible) monovalent salt concentrations.

It is well documented that in polyelectrolyte solutions a fraction of the counterions condensed along the polyelectrolytes to decrease their electrostatic energy . This ion condensation is crucial to understand the precipitation and redissolution transitions. In this paper we compute the fraction of condensed ions as the multivalent salt concentration increases in the two possible polyelectrolyte conformations: collapsed and expanded. Our two state model is based on the fact that in salt free and/or low ionic strength solutions, ion condensation leads to two possible conformation in linear flexible polyelelctrolytes: expanded-stretched with a reduced effective charge and collapsed nearly neutral with the cohesive energy of an ionic glass. Indeed, multivalent counterions lead to large cohesive energies for nearly neutral collapsed structures in region B explaining the transition L2. Since the magnitude of the electrostatic energy of a collapsed chain in region B is much larger than any entropic energy increase (due to the decrease of degrees of freedom resulting from the compaction), our model also describes the precipitation of semiflexible and rigid-rod polyelectrolytes into toroids and bundles, respectively, explaining the universality of the precipitation transition discussed in our previous work.

At the precipitation transition we predict that the expanded chains are slightly charged, and with further addition of multivalent salt, the collapsed chains (in region B) become practically neutral, in excellent agreement with recent electrophoresis experiments . As a result, the aggregates interactions in the dilute regime are negligible justifying a monomolecular collapse model to describe also multi-molecular aggregation.

The effective charge and size of the expanded conformation (in region C) changes with further addition of multivalent salt. The transition L3 occurs at high salt concentrations, and in such conditions the chains are expected to obey random walk or self-avoiding walks statistics due to the screening of the electrostatic interactions . Screening is responsible of the redissolution, as suggested in various models . We show here that the redissolution is actually very sensitive to the relation between the chemical potential of the condensing multivalent particles in the solution $`\mu `$ and the inverse screening length $`\kappa `$, while nearly insensitive to the degree of flexibility and molecular weight of the polyelectrolytes. Screening, for example, may be reduced due to multivalent-monovalent ion associating in the solution, strongly affecting the effective charge of the expanded chains. We determine the effective charge of the chains as a function of $`\mu `$ and $`\kappa `$ including the finite size of the ions and the discrete nature of the charge distribution along the polyelectrolyte, which is essential to compute the electrostatic energies of both the collapsed and expanded states. In a $`\mu \kappa `$ diagram the collapsed region lies between two branches of expanded states: one expanded with a reduced effective charge and the other expanded with an inverted charge. In most common situations the chains precipitate and redissolve within the same branch; i.e., with a reduced effective charge of the same sign of the bare charge. Our model predicts a redissolution transition independent of polyelectrolyte concentration and describes the re-dissolution of flexible, semiflexible and rigid polyelectrolytes. Indeed, the collapsed and expanded states discussed here are akin to the multi-molecular precipitated and dissolved states, respectively, observed in many polyelectrolytes , explaining the rather universal form of the diagram, Fig. 1.

In the Section 2 we summarize the assumptions of our work, and provide a description of each of the phases of the system. In section 3 we construct the free energies of two types of representative states and in Section 4 we give the result of the free energy minimization. In Section 5 we summarize our results, compare them with experiments and emphasize the elements of the theory that have not yet been subject to experimental results. We end with a brief conclusion in section 6.

## II Theoretical model

As in our previous work , we rely in a two state description of the system. Instead of considering all possible states of the system (describing them, for example by a changing scaling exponent), we simply assume that the minimum lies in one of two extremes: collapsed or expanded conformations. The expanded conformation, however, is a function of the concentration of salt in the solution. For example, at low monovalent salt concentrations the chains are expanded rods, and at large concentrations they are expanded coils . The free counterions and solvent can be integrated out provided we take into account the electrostatic interactions between the non-condensed counterions in the solution.

The condensed (collapsed) state is treated as an ionic glass  so that its energy can be approximately calculated by techniques from solid state physics ; i.e, we assume that fluctuations play no important role and can be neglected. For a very large chain, at low enough temperatures, the bulk of the collapsed state should acquire an almost crystalline structure. The finite size of the chain, the connectivity of the monomers, and finite temperature effects must induce defects into the structure and the local structure should be glass-like, where the perfect order has not been achieved. An ionic glass structure was indeed observed in recent numerical studies of polyelectrolytes in bad solvents .

In both states of the systems, the collapsed and expanded states, it is necessary to keep track of the finite size of the counterions and monomers. This is clear in the case of the collapsed state, but even in the expanded states there is an important contribution arising from interactions with the nearest neighbors, and this energy can only be calculated by considering the finite size of the particles . For example, a naive coarse-grained model that takes into account only effective charges would assign a zero energy to a neutral cluster, while it can actually have a very strong cohesive energy. The redissolution into an expanded state occurs at high salt concentrations and the effective interactions between monomers are screened. In these conditions the energy associated with interactions between far away segments of the chain can be treated as a small perturbation with respect to that of the neutral polymer state.

The properties of the salt at different concentrations are summarized into two parameters: an effective chemical potential $`\mu `$, and an inverse screening length $`\kappa `$. We will present our results for general values of these parameters and in particular consider the case were the parameters are related by a Debye-Huckel law. We also discuss the effect of multivalent-monovalent ion association, the Bjerrum model , in the diagram.

Let us consider the series of states of a single polymer chain along a line of constant polymer concentration (line P in Fig. 1) with increasing multivalent salt concentration. We start in a state in region A with few counterions condensed. The condensed counterions lie very close to the chain, and cannot be considered as mixed in the solvent. The effective charge induces repulsions between the segments of the chain, and the chain acquires extra stiffness, making it into a rod-like structure.

When a small quantity of multivalent salt is added to the system, it dissociates, and the multivalent counterions are absorbed to the chain because the electrostatic energy to be gained from the condensation is larger (per unit charge) than that of the monovalent counterions. Furthermore, the entropic loss due to condensation is lower for the multivalent counterions. When the charge of the added salt roughly equals the bare charge of the polymers the effective charge of the chains quickly goes to zero. At this point most charges of the chain are compensated by the condensed multivalent counterions and a few monovalent ones. Since a group of charges with total charge zero has a minimal energy when they are set in a compact configuration, a collapsed conformation is acquired. This transition is of course also possible for the case of pure monovalent salt, but it requires either larger concentrations or lower temperatures to offset the entropic contributions. In other words, the determining factor for the transition is the strength of the electrostatic interaction, and the introduction of multivalent salt acts as a jump in parameter space and is not equivalent to a smooth increase in monovalent salt .

In the collapsed state the absence of uncompensated charges in the polymer reduces its solubility in water and polar solvents. It is not clear from experiments, however, whether the collapsed flexible polymers aggregate into large structures or if they form a dense solution of individually collapsed chains. Though we assume monomolecular collapse, the predicted transition points should not exhibit strong dependence on the number of chains aggregated since if the collapsed state is neutral, the residual interactions between chains (promoting or opposing multimolecular aggregates) are energetically small.

Since the collapsed structure is almost neutral, the increase in salt concentrations has little effect in the absolute value of the energy of the chain. The change in the environment affects only the interaction between the positive or negative small excess (or defect) of charge in the polymer, which would be located at the surface of the collapsed structure. The energy of the charges packed inside the structure is dominated by the interaction with their nearest neighbors and is not subject to screening (there are no floating ions between them). On the other hand, the energy of an expanded chain with non-zero effective charge will be greatly reduced by the increased screening.

For the purposes of comparison with the collapsed structures, we can consider a very rigid chain that cannot be collapsed into a compact structure. We can ignore for the moment the fact that this chain would likely form a bundle with other chains, and we can assume that we have isolated it by perhaps mechanical means. At higher multivalent salt concentrations, the rigid polymer continues absorbing ions, and thus it can become neutral and even overcharged (effective charge with opposite sign to the bare charge, as it occur in many systems ). With further increase in the amount of salt the trend can be reversed, and the chain can again become, first neutral, and then simply charged (same charge sign as the bare charge). The increase of salt concentration reduces the entropic penalty for the condensation of counterions. The counterions continue condensing into the polymer as long as there is a reduction in electrostatic energy due to the condensation. The increase in condensation stops when the typical screening length of the free counterions is of the order of the monomer separation, the free counterions can reduce their energy by associating with each other, and a fraction of them will do so instead of associating with the polymer.

At large salt concentrations, the chain reverts from collapsed to expanded, giving the transition $`BC`$. In the expanded state the chain needs not to be neutral. The screening of electrostatic interaction under these conditions strongly reduces the interaction between the uncompensated charge of the polymer, and it is clear that the repulsions will not be strong enough to create a rod-like state. In these conditions an expanded coil state is more likely. In terms of the effective charge of the polymer we find that two scenarios are in principle possible. If the chemical potential of the counterions in the solvent is low enough while the screening length is reduced, the expanded state is overcharged since there is an effective decrease of energy by increasing the condensation to the chain, as recently discussed by Nguyen et al. . On the other hand, when the screening length is small, it is possible that the interactions between coions and counterions in the solvent become important, and it is much harder for the chain to acquire the counterions. This is, the chemical potential for the extraction of counterions from the solvent is large and therefore the effective charge at the redissolution point has the same sign as the bare charge. We show in the next section that though there is a possibility for overcharged polyelectrolytes at the redissolution, in the sense that this state can be preferred to a collapsed one, the salt properties required for this situation ($`\mu `$, $`\kappa `$) are unlikely to be realized in practice for water soluble multivalent ions.

## III Calculation of free energies

We assumed that the polymers are monodisperse with monomer number $`N`$. Each monomer is charged positively, and is monovalent. The original counterions of the polymer also have valence $`1`$. The polymer density is $`\varphi `$. We measure all distances with respect to the monomer size $`b`$ (so that $`b=1`$ in our units). It is necessary for more precise calculations to also give more detailed geometrical information such as the aspect ratio of the monomers and the respective size of all the ions. Here we only need to further consider, besides the size of the monomer, the radius of the multivalent counterions $`a`$. The monovalent salt concentration $`s`$ is set equal to zero, but there are monovalent counterions originally dissociated from the polymer with density $`\varphi `$, and the multivalent salt, with valences $`z:1`$ has concentration $`m`$. All energies are measured in units of $`k_BT`$, (the Boltzmann constant times the temperature), and consider only energies per monomer. We form the dimensionless Bjerrum number $`B`$, equivalent to the Manning parameter, as

$$B=\frac{e^2}{4\epsilon _0\pi bk_BT},$$
(1)
where $`\epsilon _0`$ is the permitivity of the solvent (water). The typical value of this number at room temperature in strongly charged polyelectrolytes is larger than $`1`$ and as high as $`4.2`$ for double stranded DNA. We assume here for simplicity that $`B`$ is a constant, independent of the number of locally associated monomers and ions. Given that in both states water is always present, the corrections in the values of $`ϵ`$ are expected to be minor .

In both expanded and collapsed states we describe the system by a particular geometry and a given fraction $`x`$ of condensed charge. The free energy is separated into a contribution from the solvent and free ions, and another part from the interaction of the monomers and charges condensed to them. The fraction condensed is obtained self-consistently from minimization over all possible condensed fractions. The form of the entropic term is the same in both cases, but it is easier to consider the electrostatic contributions separately.

### A Free counterions contributions

It is convenient to separate the region occupied by the polymer from the rest of the solvent. To calculate the free energy of the solvent region, we first calculate the entropic contribution. We assume that the charge condensed to the chain $`xN`$ is composed by $`x_sN`$ monovalent ions and $`x_mN/z`$ multivalent ions. Thus there are $`(s/\varphi )+1x_s`$ free monovalent counterions per monomer, and thus the energy per monomer in $`k_BT`$ units is

$$F_{s1}=(\frac{m}{\varphi }\frac{x_m}{z})\mathrm{ln}(mx_m\frac{\varphi }{z})+(\frac{s}{\varphi }+1x_s)\mathrm{ln}(s+(1x_s)\varphi ).$$
(2)
In this expression we omitted the contribution of the ions with the same charge of the monomers, since it is assumed that they do not condense, and thus have a constant contribution. We have also omitted the contribution of the solvent, since the concentration of the salts is small compared to the solvent. It is possible to add in this expression an interaction term between the solvent and the ions, but for simplicity we neglect these corrections here; its effect would be only to shift the position of the L3 line in the phase diagram. It is important to consider, however, the effective free energy of interaction between all free ions. A simple way to do this is to use the modified Debye-Huckel form:

$$F_{s2}=\frac{1}{4\pi \varphi }\left(ln(1+\kappa a)\kappa a+\frac{1}{2}(\kappa a)^2\right).$$
(3)
In this expression $`a`$ is the hard-core radius of the salt ions and $`\kappa `$ is the inverse screening length produced by the salt:

$$\kappa ^2=4\pi B(z^2(mx_m\varphi /z)+zm+(2s+(1x_s)\varphi )).$$
(4)
In the very dilute polymer limit, we can simplify these expressions, and use instead

$$\kappa ^2=4\pi z(z+1)Bm,$$
(5)
and expand the total free energy of the solvent $`F_s=F_{s1}+F_{s2}`$ in a series in the overcharge fraction $`y=x1`$. The constant term is irrelevant and we retain only the linear term:

$$F_s=(_yF_s)y=\mu y,$$
(6)
where $`\mu `$ is now the effective chemical potential for the extraction of ions from the solvent into the condensed region. Using the same high salt limit as before we obtain:

$`\mu ={\displaystyle \frac{1}{z}}\mathrm{ln}m+{\displaystyle \frac{1}{8\pi (z+1)m}}{\displaystyle \frac{\kappa ^3}{1+\kappa a}}.`$

### B Expanded state energy

In our previous work , we considered only the energy of rod-like conformations. Since our interest is the regime with large amounts of salt, the screening strongly reduces the rigidity of the chain due to excess charge. It is then adequate to consider a Gaussian conformation (self-avoiding walk conformations give very similar results, as it can be seen from the functional form of the free energy computed below). The electrostatic contribution to the free energy is calculated as a function of the condensed charge, and we set the neutral state $`x=1`$ as reference. The free energy is expressed as the sum of three terms. A constant term reflects the energy of the neutral state, a term linear in the excess charge $`y=(x1)`$ appears due to addition or extraction of a charge into or from the neutral state. Finally, the interaction between segments of the chain with excess charge gives rise to a term quadratic in $`y`$. We write this as:

$$F_e^e=g_0^e+g_1^ey+g_2^ey^2.$$
(7)
A coarse-grained model clearly gives rise to the last term, and the first two can be understood, in that context, as regularizations that take into account the finite size of the particles involved. In the limit of large amounts of salt-added, most of the condensed charge comes from multivalent ions, and thus, we will take $`x=x_m`$, and $`x_s=0`$. The terms are graphically represented in Fig.2.

For the calculation of the energy of the neutral state we basically apply the Wigner principle: in a dense ionic system, the free energy can be approximated by the contribution of nearest neighbors that effectively cancel the charge of the particle. In the case of the collapsed state, below, it is more suitable to consider an approximation based on the calculation related to a full infinite lattice.

The basic neutral cluster of the linear polyelectrolyte consists of one multivalent counterion, and $`z`$ monomers. Since all particles in the cluster (with charges $`q_I`$, both monomers at distances $`r_{ij}`$ from each other, all roughly equal to the monomer size $`r=b=1`$, the electrostatic energy of the cluster is

$$E=\underset{ij}{}B\frac{q_iq_j}{r_{ij}}=B(z^2+z(z1)/2)$$
(8)
Dividing by $`z`$ monomers, we obtain:

$$g_0^e=B(z+1)/2.$$
(9)
When an extra multivalent ion is added to this cluster, the counterion can have roughly the same interaction with the chain monomers, but can locate itself away of the first counterion, say, by putting a monomer in between them so that $`r2`$. Thus we obtain a simple estimate for the energy of the new charged cluster as:

$$E=B(2z^2+z(z1)/2+z^2/2),$$
(10)
and

$$g_1^e=Bz/2.$$
(11)
Finally, the two-body term can be calculated assuming a uniform distribution of charge along the Gaussian chain. A Gaussian chain has a monomer distribution given, approximately, by $`\rho (r)=1/(2\pi r)`$, inside the volume $`V`$ limited by the radius of gyration $`R`$; this is, for $`r<R=N^{1/2}`$. A charge at the center of this distributions interacts with other charges via the screened potential $`Be^{\kappa r}/r`$. The energy for one such charge is given by the average over the volume $`V`$ of this potential:

$$E=V=_V𝑑𝐫\rho (r)B\frac{e^{\kappa r}}{r}=\frac{B}{\kappa }(1e^{\kappa R}),$$
(12)
and by our previous definition,

$$g_2^e=\frac{1}{2}V.$$
(13)
Notice that while this calculation depends on the assumed Gaussian conformation, a simple estimate can also be done by using a general expansion coefficient for the radius of gyration $`RN^\nu `$, ($`\nu =1`$ for rod-like, $`\nu =2/3`$ for self-avoiding walks, and $`\nu =1/2`$ for random walks). In such case, we obtain a scaling for the quadratic precoefficient of the form $`g_2^e\kappa ^{(11/\nu )}`$. While these different models give rise to different estimates, the transition we are interested in occurs when the screening is of the order of the size of the monomers, and so, in our units, $`\kappa 1`$, and the estimates at that point are not so different.

### C Collapsed state energy

We repeat a similar approach for the calculation of the free energy of the collapsed state which is expressed as:

$$F_e^c=g_0^c+g_1^cy+g_2^cy^2.$$
(14)
Inside the collapsed polymer, we can imagine the environment of a charge resembling that of a ionic crystal. If the structure of the crystal is known, the energy per atom in that crystal can be given in terms of the Madelung constant ,

$$E=Me^2/r=MB.$$
(15)
The Madelung constant for an ionic monovalent salt is $`M=1.747`$. There are two important differences in our case. We would like to consider multivalent ions, which reduce the contribution from same-charge interactions, and on the other hand the connectivity of the monomers forces them to be next-neighbors (not the case in ionic crystals), and thus increases the same-charge interactions. A way to obtain a rough estimate for $`M`$ is to consider a simple geometry in which both monomers and counterions lie in columns which in turn form a square lattice when a cross section is taken. The result does not change dramatically when other possible geometries are considered. As a rule of thumb, we can use an effective Madelung constant that is larger than unity, but not much bigger. In the geometry proposed, the number of next neighbors of counterion is $`4z`$. Summing the interaction with $`4z`$ monomers and 4 equally charged next-nearest counterions ($`r=2b`$) we obtain the following estimate of the energy per cluster of $`1`$ counterion and $`z`$ monomers:

$$E=B(4z^2+z(z1)+\frac{1}{2}z(4zz)+\frac{1}{2}\frac{4z^2}{2})$$
(16)
where the interactions with charges outside the cluster are weighted by $`1/2`$ to avoid double counting. Dividing again by $`z`$, we obtain the coefficient of the energy per monomer:

$$g_0^c=B(1+\frac{z}{2}).$$
(17)
In this approximation we have underestimated the Madelung constant for $`z=1`$, for which we obtain $`1.5`$ instead of the exact result $`1.747`$, but it is a reasonable approximation and shows that the energy of this neutral collapsed state is smaller than the neutral expanded state.

In both the collapsed and expanded states, the addition and extraction of charges are not completely symmetric processes. It is energetically unfavorable to add or extract charges from the collapse bulk state, as shown below in the calculation of $`g_2^c`$. Both processes are however better thought of as occurring at the surface of the collapsed region. We have also argued previously , that while the mobility of charges in this type of conformations is not so large, the analogy with a conductor is still useful: all charge excess resides in the surface. While the local conformation at the surface of the collapsed state is not equal to the expanded state, it is simpler to borrow the result for the coefficient related to the addition of one charge from that case. In both situations the new charge is put in close contact with a neutral cluster, but sits slightly closer to the opposite charges. Thus,

$$g_1^c=Bz/2.$$
(18)
Since we assume that the extra charge is sitting at the surface, the interaction energy can be calculated assuming a uniform distribution in a shell surrounding the collapsed polymer. We assume this shell to be spherical with radius $`R`$, and obtain the energy per added charge as

$$g_2^c=E=\frac{1}{2}B\frac{1}{R}=\frac{1}{2}\frac{B}{(3N(1+1/z)/4\pi )^{1/3}}$$
(19)
Here we have considered that the $`N+N/z`$ charged particles are closely packed and that they occupy each a volume of $`b^3`$.

## IV Comparison between states and Phase diagram

After the minimization of the free energies of each state with respect to their respective condensed charge variables, we can compare each other to find the state of the chain for given concentration conditions. This minimization can be done directly from the expressions already given but it is easier to present simpler formulas if we use a set of approximations described below. Numerical results presented later reflect these approximations, but we have checked that numerical minimization of the full expressions do not lead to important qualitative and quantitative changes in the results.

The free energy of each of the states, for given concentrations of monomers and salt correspond to the minima of:

$`F^e`$ $`=`$ $`F_s+F_e^e,`$ (20)
$`F^c`$ $`=`$ $`F_s+F_e^c`$ (21)
for the expanded and collapsed states respectively. We minimize now with respect to the overcharge fraction $`y`$.Taking the first derivatives with respect to this quantity, we obtain the (independent) conditions

$`_yF^e`$ $`=`$ $`\mu +g_1^e+2g_2^ey^e=0,`$ (22)
$`_yF^c`$ $`=`$ $`\mu +g_1^c+2g_2^cy^c=0.`$ (23)
The solutions for the fractions condensed are:

$`y^e`$ $`=`$ $`(\mu +g_1^e)/2g_2^e,`$ (24)
$`y^c`$ $`=`$ $`(\mu +g_1^c)/2g_2^c.`$ (25)
Replacement of this values in the general expressions for the free energy gives the minimized free energies for each state:

$`F^e`$ $`=`$ $`F^e(y^e)=\mu +g_0^e{\displaystyle \frac{(g_1^e+\mu )^2}{4g_2^e}},`$ (26)
$`F^c`$ $`=`$ $`F^c(y^c)=\mu +g_0^c{\displaystyle \frac{(g_1^c+\mu )^2}{4g_2^c}}.`$ (27)
For the moment it is convenient to maintain the expressions of the free energies as functions of the chemical potential instead of the salt concentration. Of the parameters used to describe the different states, only $`g_2^e`$ has an explicit dependence on the concentration (through the inverse screening length $`\kappa `$)l. Also, it is important to note that the coefficient $`g_2^c`$ is extremely large, and for the values of the chemical potential that we need to explore, it turns out that the denominator in the expression for the overcharge is much larger than the numerator, and the overcharging fraction is very close to $`0`$:

$$y^c0.$$
(28)
This result is clear since we have found that there is a very strong penalty for any overcharging (or undercharging) in the collapsed state. The effective charge in a general structure is affected by the environment (namely, by $`\mu `$) but the collapsed structure is only very slightly susceptible to it. Furthermore, the interaction between the charges in the bulk of the collapsed structure is not subject to screening by the free particles outside and its contribution remains constant with changing chemical potential. Thus, the system splits neatly into collapsed neutral structures and a homogeneous mixture of solvent and non-condensed counterions. It is then not surprising that this state adequately represents what in experiment is close to be two separate phases.

Consider now the minimum for the expanded state. The coefficient for charge-charge interactions $`g_2^e`$ varies very strongly with the salt concentration. It remains large when the screening length is large, since in those conditions all uncompensated charges interact strongly. On the other hand at large concentrations of salt the screening drastically reduces the interaction between segments of the chain.

To obtain an expression for the transition point we subtract the free energies, and define the energy difference

$$\mathrm{\Delta }F=F^eF^c.$$
(29)
The system is in the region $`B`$, when $`\mathrm{\Delta }F>0`$, in region $`C`$ when $`\mathrm{\Delta }F<0`$, and the transition curve is defined by $`\mathrm{\Delta }F=0`$. Using the fact, discussed above, that the electrostatic energy of the collapsed state remains essentially constant, we can write the equation $`\mathrm{\Delta }F=0`$ as

$$g_0^e\frac{(g_1^e+\mu )^2}{4g_2^e}=+g_0^c.$$
(30)
One useful way to use and interpret this equation is to consider it as defining a boundary in the $`\mu \kappa ^2`$ plane that corresponds to the properties of the counterions. Within this diagram, a particular form of the relation between concentration and screening for a counterion defines a path in the diagram parametrized by the salt concentration $`m`$. Examples of this are presented in Fig.3. for certain polymer properties values, and different types of $`\mu \kappa ^2`$ relations.

At this point is very easy to explain the observed near independence of the transition on the molecular weight of the chains. Only the coefficients $`g_2`$ carry information on the molecular weight, but as we have seen $`g_2^c`$ drops out of the final equations, and in $`g_2^e`$ the molecular weight provides only an exponentially small correction to the dominant term given by a function of the screening length.

As shown in Fig.3, and as it can be seen from the fact that the equations defining the transition are quadratic in $`\mu `$, the expanded state splits into two regions, each with non-zero effective charge, but with opposite signs on each. This diagram is obtained using the approximations presented above, and a more precise determination of the lines of transition will involve consideration of the monovalent counterions, the finite amount of monomers, and the rod-like state obtained at very low screening. When these considerations are taken into account, the trajectory described by the added salt in the $`\mu \kappa ^2`$ plane will start within the expanded region, cross into the collapsed region (giving rise to the L1-L2 line), and continue there until crossing again, redissolving, into one of the branches with expanded states. The starting point of the trajectory, with zero multivalent salt added $`m=0`$, is located in the branch with natural charge, at a finite $`\kappa `$ value (due to the monovalent counterions), and at $`\mu =\mathrm{}`$. Figure 3 illustrates only the redissolution.

In Fig.3 we show three different curves defining the properties of the counterions: a pure Debye-Huckel case where the size of the counterions are neglected, a modified Debye-Huckel curve with $`a=0.2`$ (that is $`a=0.2b`$), and a third curve that neglects the interactions between the counterions when they are free considers only the entropic term. The reversal of direction in the $`\mu `$ axis of the parametric curve for the Debye-Huckel cases occurs because of the onset of important favorable interactions between the free charges. Thus it is clear that the trajectory can end in the naturally charged branch of the expanded region since there are more free counterions there, and at the same time the repulsive intra-chain interactions are small. The overcharged branch is only accessible if the chemical potential is further reduced at the same time that the screening increases. For most cases with sensible sizes for the counterions the reversal in direction of the parametrized curve comes always before the redissolution, and thus the redissolution is into the naturally charged state.

It is interesting to note that at high enough salt concentrations and high valences, the salt might re-associate on its own. In this case the trajectory in the $`\mu \kappa ^2`$ plane has a different shape than that provided by the Debye-Huckel equation. Indeed, while the results from the Debye-Huckel model are know to provide good approximations for the free energy of the salt in solution they do not properly describe the individual dissociated species. The upturn of the chemical potential essentially indicates a phase transition for the salt/solvent system. In reality there is no phase transition but there is a finite a fraction of ion pairs formed in the solvent (even if they do not reassociate chemically). We have not presented here the curve in the $`\mu \kappa ^2`$ diagram when the association of multivalent ions in the solution is present, as is modeled, for example, in the classical Bjerrum model , or more recently by Fisher, et al. This association gives large corrections to the Debye-Huckel law (for the free energy of the individual species of ions) and in our case provides a $`\mu \kappa `$ curve that monotonically approaches a horizontal line (a limiting $`\mu `$ value), with increasing inverse screening length. These effects are particularly important for large valence salts as in our case and we will discuss them in more detail in a future publication .

## V Comparison with experimental information

With the previously obtained solutions we now contrast our results with the currently known experimental situation. We consider the shape of the phase diagram, the precise location of the collapse transition and the predicted structure of the polymers in both of the phases.

It should be clear that we have already recovered the shape of the $`B`$-$`C`$ transition. Indeed, the (approximate) equation that define the transition does not have any dependence on the monomer concentration, and therefore produces a flat line in the $`\varphi m`$, or $`\varphi \mu `$ diagrams. The transition is defined by the choice of single chains to be in one of two states that must be in equilibrium with the surrounding environment. This environment, represented here by means of an effective chemical potential and screening length, depends strongly on the amount of multivalent salt and only very slightly on the polymer amount. The more precise expressions for the chemical potential recovers a small dependence in the polymer concentration.

There are two important ways in which important changes on the qualitative form of the diagram can arise.The addition of large amounts of monovalent salt introduces new features in the phase diagram, not show in the scheme of Fig. 1. In the introduction we only mentioned the effects on the $`AB`$ transition, but further addition of monovalent salt, creates a different environment of the chains, and changes the transition points and the shape of the transition curve. Secondly, it is clear that as we continue increasing the amount of polymer in the solution, the interactions between the chains start to become important and the transition (if any) is a much more complicated phenomena. From the point of view of our theory it is clear that the increase in concentration of monovalent salt and monomers bring about a breakdown of the assumption that the chemical potential for the overcharging is dependent only on the amount of multivalent salt. The effective environment of the chain becomes more complicated and the chemical potential will now contain important terms coming form the concentrations of all species and from many-body interactions.

Let us consider two concrete numerical examples. Experiments performed on polystyrene sulfonate  at room temperature with $`N=410^3`$, Bjerrum number of $`B=2.87`$ ($`b=0.5`$ nm) and an effective ion radius $`a/b=0.2`$, show a transition line at a concentration of $`m=0.2M`$ of $`LaCl_3`$. With these parameters as input, our equation predicts redissolution at a salt concentration of $`m=0.1M`$. Secondly, experiments on double stranded DNA  with very large number of base pairs (we take $`N=10^4)`$ and $`B=4.2`$ ($`b=.17`$ nm)in spermine ($`z=4`$), $`a=1`$. obtained redissolution at $`m=.1M`$, while our equations predict a transition at $`m=0.04M`$. This compares favorably with the experiments, especially if we take into account the rough approximations done in the evaluation of the energies of the system.

According to the theory presented, in phase B, the polymer chains are almost neutral with a collapsed conformation. In phase C, the chains are expanded and charged. This suggests, besides other techniques, to confirm these predictions by means of scattering experiments that test the structure of the chains, and of osmotic pressure measurements that can determine the amount of free counterions in each state (as it has been done for semi-dilute solutions).

## VI Conclusions

The redissolution transition observed in multivalent induced precipitated polyelectrolytes with further addition of multivalent particles or salt was predicted extending a previously developed two state model to deal with large salt concentrations. The electrostatic energies of both, collapsed and expanded-coiled, states were computed considering the finite size of the ions and monomers condensed along the chains, and using a mean field approach for the non-condensed ions. We neglected the non-ionic short range interactions of the ions with the solvent, and assume zero monovalent salt.

We found that the redissolution is determined by the properties of the ionic solution. We calculated the effective charge of the chains for the different thermodynamic states of the chain.

### Acknowledgments

We thank E. Raspaud and F. Livolant for useful discussions and for performing electrophoresis experiments , M. Campos for computing electrostatic energies of dense finite size systems of charges, and P. A. Bernikowicz for computing the free energy of aggregates containing $`p=1,2,\mathrm{}`$ chains. This work was sponsored by the National Science Foundation, grants DMR9807601 and DMR9632472.


text:
# Finite Temperature Excitations of an Inhomogeneous Trapped Bose Gas With Feshbach Resonances*footnote **footnote *Mailing address: Institute of Theoretical Physics, Academia Sinica, Peking 100080, China

## Abstract

We derive and discuss the temperature dependance of the condensate and noncondensate density profile of a Bose-Einstein condensate gas with Feshbach resonance in a parabolic trap. These quantities are calculated self-consistently using the generalized Hartree-Fock-Bogoliubov (HFB) equations within the Bogoliubov approximation. At zero temperature, the HFB equation can be solved by means of a variation method that give the low excitation spectrum. Moreover, within the two-body collision theory, we estimate the relationship between the atom number and the external magnetic field $`B`$, it is in good agreement with the data in recent experiments.

Bose-Einstein condensates\[1-4\] of atomic gases offer new opportunities for studying quantum-degenerate fluids. Almost all the essential properties of Bose-Einstein condensate systems such as the formation and shape of the condensate and noncondensate, the nature of its collective excitations and statistical fluctuations, and the formation and dynamics of vortices are determined by the strength of atom-atom interactions. In contrast with the situation in traditional superfluids, the strength of inter-particle interactions in the atomic condensate can vary over a wide range of values\[5-12\]. In particular, the scattering length that characterizes the atom-atom interactions can be negative, corresponding to an effective inter-atom attraction.

Most recently, in trapped atomic Bose-Einstein condensation, Ketterle’s group reported evidences for modifying the scattering length by magnetic-field-induced Feshbach resonance. Feshbach resonance have been studied twenty one years ago at much higher energies, but the Feshbach resonance energy observed in ultracold atoms can be tuned to near zero. The theoretical studies of the ultracold atoms with Feshbach resonance show that the two-body interactions responsible for the Feshbach resonance produce an additional condensate of molecules, which differs qualitatively from the properties of a single condensate. In this letter, we discuss the temperature dependance of the hybrid atomic/molecular condensate and noncondensate density profile as well as the excitation spectrum. Especially, for an inhomogeneous system with negative scattering length, the excitation spectrum shows a upper constraint on the atom number, which, together with the conventional estimation of the condensate atom number, gives the relationship between the atom number and the external magnetic field $`B`$. The theoretical results are in good agreement with the experiment.

The binary atom Feshbach resonances studied by varying a strong external magnetic field in an alkali-atom trap are hyperfine-induced spin-flip processes that bring the colliding atoms to a bound molecular state of different electron spin. This process can be described by the Hamiltonian

$$H_{FR}=\alpha d^3r\mathrm{\Psi }_m^+(r)\mathrm{\Psi }_a(r)\mathrm{\Psi }_a(r)+h.c.,$$
(1)
where $`\mathrm{\Psi }_m(r),\mathrm{\Psi }_m^+(r)`$ ($`\mathrm{\Psi }_a(r),\mathrm{\Psi }_a^+(r)`$) are the annihilation and creation field operators of the molecules(atoms), $`\alpha `$ stands for the transition matrix element proportional to the overlap of the molecular continuum and bound state wave functions. Usually, the transition matrix element depends on the magnetic field as $`\alpha \sqrt{\lambda _a\mathrm{\Delta }^2/2|BB_0|}`$, where $`B_0`$ is the resonant magnetic field and $`\mathrm{\Delta }`$ characterizes the width of the resonance as a function of $`B`$. The Hamiltonian $`H_{FR}`$ together with the atomic Hamiltonian

$$H_a=d^3r\mathrm{\Psi }_a^+(r)[\frac{^2}{2M}+V_a(r)\mu _a]\mathrm{\Psi }_a(r)+\frac{\lambda _a}{2}d^3r\mathrm{\Psi }_a^+(r)\mathrm{\Psi }_a^+(r)\mathrm{\Psi }_a(r)\mathrm{\Psi }_a(r),$$
(2)
the molecular Hamiltonian

$$H_m=d^3r\mathrm{\Psi }_m^+(r)[\frac{^2}{4M}+V_m(r)\mu _m+ϵ]\mathrm{\Psi }_m(r)+\frac{\lambda _m}{2}d^3r\mathrm{\Psi }_m^+(r)\mathrm{\Psi }_m^+(r)\mathrm{\Psi }_m(r)\mathrm{\Psi }_m(r),$$
(3)
and the atom-molecule interaction Hamiltonian

$$H_{am}=\lambda d^3r\mathrm{\Psi }_a^+(r)\mathrm{\Psi }_m^+(r)\mathrm{\Psi }_m(r)\mathrm{\Psi }_a(r)$$
(4)
forms a total Hamiltonian $`H=H_a+H_m+H_{am}+H_{FR}`$, which governs the dynamics of the system under investigation. Here, $`V_{a(m)}(r)`$ represents the trapped potential for atom (molecule), $`\mu _{a(m)}`$ is the chemical potential of the atoms(molecules), $`\lambda _{a(m)}=\frac{4\pi a_{a(m)}}{(2)M}`$, with $`M`$ being the atomic mass and $`a_{a(m)}`$ the s-wave scattering length of the atom-atom interaction, $`\lambda `$ denotes the coupling constant of the atom-molecule interaction, and $`ϵ`$ is the energy of the intermediate molecular state relative to the continuum of the incident atoms.

Separating out the condensate part in the usual fashion (Bogoliubov approximation) i.e.

$$\mathrm{\Psi }_{a(m)}(r)=\varphi _{a(m)}(r)+\widehat{\phi }_{a(m)}(r),$$
(5)
where $`\varphi _{a(m)}(r)=\mathrm{\Psi }_{a(m)}(r)`$ plays the role of a spatially varying macroscopic Bose field of the atoms(molecules). The possibility that the resonantly formed quasibound atom pairs form a molecular condensate was previously suggested by Timmermans et al.. Using a Raman photonassociation process, the quasibound pairs start to be formed from the atomic condensate and form a molecular condensate. Here, we assume that there are a large number of atoms and molecules in the condensate. It is easy to show that the operators $`\widehat{\phi }_{a(m)}(r)`$ and $`\widehat{\phi }_{a(m)}^+(r)`$ obey the Bose commutation relations

$$[\widehat{\phi }_{a(m)}(r),\widehat{\phi }_{a(m)}^+(r^{})]=\delta (rr^{}).$$
(6)
In terms of $`\widehat{\phi }_{a(m)}`$ and $`\varphi _{a(m)}`$, the Hamiltonian can be expanded as

$`H`$ $`=`$ $`H_0+H^{^{}},`$ (7)
$`H_0`$ $`=`$ $`{\displaystyle }d^3r\{\varphi _a^{}({\displaystyle \frac{^2}{2M}}\mu _a+V_a(r))\varphi _a+{\displaystyle \frac{\lambda _a}{2}}\varphi _a^{}\varphi _a^{}\varphi _a\varphi _a`$ (8)
$`+`$ $`\varphi _m^{}({\displaystyle \frac{^2}{4M}}\mu _m+V_m(r)+ϵ)\varphi _m+{\displaystyle \frac{\lambda _m}{2}}\varphi _m^{}\varphi _m^{}\varphi _m\varphi _m`$ (9)
$`+`$ $`\lambda \varphi _a^{}\varphi _a\varphi _m^{}\varphi _m+\alpha \varphi _m^{}\varphi _a\varphi _a+\alpha \varphi _m\varphi _a^{}\varphi _a^{}\}`$ (10)
$`H^{^{}}`$ $`=`$ $`{\displaystyle }d^3r\{\widehat{\phi }_a^+({\displaystyle \frac{^2}{2M}}\mu _a+V_a(r))\widehat{\phi }_a+2\lambda _a\widehat{\phi }_a^+\widehat{\phi }_a\varphi _a^{}\varphi _a+{\displaystyle \frac{\lambda _a}{2}}(\widehat{\phi }_a^+\widehat{\phi }_a^+\varphi _a\varphi _a+\widehat{\phi }_a\widehat{\phi }_a\varphi _a^{}\varphi _a^{})`$ (11)
$`+`$ $`\widehat{\phi }_m^+({\displaystyle \frac{^2}{4M}}+ϵ\mu _m+V_m(r))\widehat{\phi }_m+2\lambda _m\widehat{\phi }_m^+\widehat{\phi }_m\varphi _m^{}\varphi _m+{\displaystyle \frac{\lambda _m}{2}}(\widehat{\phi }_m^+\widehat{\phi }_m^+\varphi _m\varphi _m+\widehat{\phi }_m\widehat{\phi }_m\varphi _m^{}\varphi _m^{})`$ (12)
$`+`$ $`\lambda \widehat{\phi }_a^+\widehat{\phi }_a\varphi _m\varphi _m^{}+\lambda \widehat{\phi }_m^+\widehat{\phi }_m\varphi _a^{}\varphi _a+\alpha (\widehat{\phi }_a\widehat{\phi }_a\varphi _m^{}+\widehat{\phi }_a^+\widehat{\phi }_a^+\varphi _m)\}.`$ (13)
In derivation of eq.(7,8), the following coupling equations are used,

$`\{{\displaystyle \frac{^2}{2M}}+\lambda _a|\varphi _a|^2+V_a(r)+\lambda |\varphi _m|^2\}\varphi _a+2\alpha \varphi _m\varphi _a^{}=\mu _a\varphi _a,`$ (15)
$`\{{\displaystyle \frac{^2}{4M}}+\lambda _m|\varphi _m|^2+V_m(r)+ϵ+\lambda |\varphi _a|^2\}\varphi _m+\alpha \varphi _a\varphi _a=\mu _m\varphi _m.`$ (16)
This coupling equations may be yielded by the expectation value of the Heisenberg equations

$$i\mathrm{}\dot{\mathrm{\Psi }}_a=[\mathrm{\Psi }_a,H],i\mathrm{}\dot{\mathrm{\Psi }}_m=[\mathrm{\Psi }_m,H],$$
(17)
and replacing the time derivatives by the chemical potentials

$$i\mathrm{}\dot{\varphi }_a\mu _a\varphi _a,i\mathrm{}\dot{\varphi }_m\mu _m\varphi _m.$$

The chemical potential of the molecules is twice the chemical potential of the atoms, in accordance with the condition for chemical equilibrium. The $`\alpha `$terms that couple the equations describe tunneling of pairs of atoms between $`\varphi _m`$ and $`\varphi _a`$ fields, it leads to the form of a second condensate—molecular condensate in an atomic Bose-Einstein condensate\[15-17\]. Using the coupling equations(9), Timmermans et al. investigate the behaviors of the hybrid atomic/molecular condensates near- and off- resonance. The Hamiltonian (8) can be diagonalized by using the Bogoliubov transformation

$`\widehat{\phi }_a(r)={\displaystyle \underset{j}{}}[u_j(r)\alpha _jv_j^{}(r)\alpha _j^+],`$ (18)
$`\widehat{\phi }_a^+(r)={\displaystyle \underset{j}{}}[u_j^{}(r)\alpha _j^+v_j(r)\alpha _j],`$ (19)
$`\widehat{\phi }_m(r)={\displaystyle \underset{j}{}}[x_j(r)\beta _jy_j^{}(r)\beta _j^+],`$ (20)
$`\widehat{\phi }_m^+(r)={\displaystyle \underset{j}{}}[x_j^{}(r)\beta _j^+y_j(r)\beta _j],`$ (21)
where the qusiparticle operators $`\alpha _j`$,$`\alpha _j^+`$,$`\beta _j`$, $`\beta _j^+`$ obey boson commutation relations

$$[\alpha _i,\alpha _j^+]=\delta _{ij},[\alpha _i,\alpha _j]=[\alpha _i^+,\alpha _j^+]=0,$$

$$[\beta _i,\beta _j^+]=\delta _{ij},[\beta _i,\beta _j]=[\beta _i^+,\beta _j^+]=0,$$

$$[\alpha _i^+,\beta _j^+]=[\alpha _i,\beta _j]=[\alpha _i,\beta _j^+]=0,$$

and $`u_j(r),v_j(r),x_j(r),y_j(r)`$ are $`c`$-number functions. Substituting eq.(11) into eq.(8), one yields

$$H^{^{}}=\underset{j}{}E_j\alpha _j^+\alpha _j+\underset{i}{}e_i\beta _i^+\beta _i\underset{j}{}E_jd^3r|v_j(r)|^2\underset{i}{}e_id^3r|y_i(r)|^2$$
(22)
with

$`({\displaystyle \frac{^2}{2M}}+\lambda |\varphi _m|^2+2\lambda _a|\varphi _a|^2\mu _a+V_a(r))u_j(\lambda _a\varphi _a^{}\varphi _a^{}+2\alpha \varphi _m^{})v_j`$ $`=`$ $`E_ju_j,`$ (23)
$`({\displaystyle \frac{^2}{2M}}+\lambda |\varphi _m|^2+2\lambda _a|\varphi _a|^2\mu _a+V_a(r))v_j(\lambda _a\varphi _a^{}\varphi _a^{}+2\alpha \varphi _m^{})u_j`$ $`=`$ $`E_jv_j,`$ (24)
$`({\displaystyle \frac{^2}{4M}}+ϵ+\lambda |\varphi _a|^2+2\lambda _m|\varphi _m|^2\mu _m+V_m(r))x_j\lambda _m\varphi _m^{}\varphi _m^{}y_j=e_jx_j,`$ (25)
$`({\displaystyle \frac{^2}{4M}}+ϵ+\lambda |\varphi _a|^2+2\lambda _m|\varphi _m|^2\mu _m+V_m(r))y_j\lambda _m\varphi _m^{}\varphi _m^{}x_j=e_jy_j.`$ (26)
In order to study the temperature dependence of the excitation spectrum as well as the spatial distribution of the hybrid atom/molecular condensate and noncondensate, we need to solve the coupled mean-field Bogoliubov equations(13), and the condensate equation(9) self-consistently. The calculations procedure can be summarized for an arbitrary confining potential as follows: First of all, we solve eq.(9) self-consistently, once $`\varphi _a`$ and $`\varphi _m`$ are known, the solution of $`u_j,v_j,x_j`$ and $`y_j`$ can be generated. To illustrate this procedure, we present its first step of calculations analytically. The trapped potential considered here is taken to be an isotropic harmonic potential $`V_{a(m)}(r)=\frac{1}{2}M\omega _{a(m)}^2r^2`$, for which $`\varphi _a`$ and $`\varphi _m`$ are spherically symmetric functions,

$$\varphi _{a(m)}(r)=R_{00}(r)Y_{00}(\theta ,\psi ),$$
(27)
with

$$R_{00}(r)=\alpha ^{3/2}\sqrt{\frac{4}{\pi }}exp[\frac{1}{2}\alpha ^2r^2],Y_{00}(\theta ,\psi )=\frac{1}{\sqrt{4\pi }},\alpha =((2)M\omega )^{1/2}.$$

Rather than solving the coupled equations (13) directly, we introduce a new method based on the auxiliary functions

$`u_j`$ $`=`$ $`A_jr|j_a,v_j=B_jr|j_a,`$ (28)
$`x_j`$ $`=`$ $`C_jr|j_m,y_j=D_jr|j_m,`$ (29)
where $`|j_{a(m)}`$ is defined by

$$[\frac{^2}{2(4)M}+V_{a(m)}(r)]|j_{a(m)}=\mathrm{}\omega _{a(m)}(j+\frac{1}{2})|j_{a(m)}.$$

The reason for such selection is that the level shifts caused by atom-atom interactions weakly depend on the shape of the wave function. A combination of Eqs.(13-15) gives

$`(\mathrm{}\omega _a(j+{\displaystyle \frac{1}{2}})+\lambda |\varphi _m|^2+2\lambda _a|\varphi _a|^2\mu _a)A_j(\lambda _a\varphi _a^{}\varphi _a^{}+2\alpha \varphi _m^{})B_j`$ $`=`$ $`E_jA_j,`$ (31)
$`(\mathrm{}\omega _a(j+{\displaystyle \frac{1}{2}})+\lambda |\varphi _m|^2+2\lambda _a|\varphi _a|^2\mu _a)B_j(\lambda _a\varphi _a^{}\varphi _a^{}+2\alpha \varphi _m^{})A_j`$ $`=`$ $`E_jB_j,`$ (32)
$`(\mathrm{}\omega _m(j+{\displaystyle \frac{1}{2}})+ϵ+\lambda |\varphi _a|^2+2\lambda _m|\varphi _m|^2\mu _m)C_j\lambda _m\varphi _m^{}\varphi _m^{}D_j=e_jC_j,`$ (33)
$`(\mathrm{}\omega _m(j+{\displaystyle \frac{1}{2}})+ϵ+\lambda |\varphi _a|^2+2\lambda _m|\varphi _m|^2\mu _m)D_j\lambda _m\varphi _m^{}\varphi _m^{}C_j=e_jD_j,`$ (34)
the eigenfunctions and the corresponding eigenvalues are given by

$`B_j^\pm `$ $`=`$ $`[{\displaystyle \frac{1}{f^\pm (r,j)1}}]^{\frac{1}{2}},A_j^\pm (r)=f^\pm (r,j)B_j^\pm ,`$ (35)
$`D_j^\pm `$ $`=`$ $`[{\displaystyle \frac{1}{g^\pm (r,j)1}}]^{\frac{1}{2}},B_j^\pm (r)=g^\pm (r,j)D_j^\pm ,`$ (36)
and

$`E_j^\pm (r)`$ $`=`$ $`\pm \{(\lambda _a\varphi _a^{}\varphi _a^{}+2\alpha \varphi _m^{})[\mathrm{}\omega _a(j+{\displaystyle \frac{1}{2}})\mu _a+\lambda |\varphi _m|^2+2\lambda _a|\varphi _a|^2]\},`$ (37)
$`e_j^\pm (r)`$ $`=`$ $`\pm \{\lambda _m\varphi _m^{}\varphi _m^{}[\mathrm{}\omega _m(j+{\displaystyle \frac{1}{2}})\mu _m+ϵ+2\lambda _m|\varphi _m|^2]\}.`$ (38)
Here,

$$f^\pm (r,j)=\frac{\lambda _a\varphi _a^{}\varphi _a^{}+2\alpha \varphi _m^{}}{\mathrm{}\omega _a(j+\frac{1}{2})\mu _a+\lambda |\varphi _m|^2+2\lambda _a|\varphi _a|^2(E_j^\pm )^2},$$

and

$$g^\pm (r,j)=\frac{\lambda _m\varphi _m^{}\varphi _m^{}}{\mathrm{}\omega _m(j+\frac{1}{2})\mu _m+ϵ+2\lambda _m|\varphi _m|^2(e_j^\pm )^2}.$$

These explicit solutions enable us to construct the one-body density matrix

$`\rho (r,r^{^{}})`$ $`=`$ $`\rho _a(r,r^{^{}})+2\rho _m(r,r^{^{}}),`$ (39)
$`\rho _a(r,r^{^{}})`$ $`=`$ $`\varphi _a^{}(r)\varphi _a(r^{^{}})`$ (40)
$`+`$ $`{\displaystyle \underset{p=\pm ,i=1}{\overset{\mathrm{}}{}}}[u_i^p(r)u_i^p(r^{^{}})F_i^p+v_i^p(r)v_i^p(r^{^{}})(1+F_i^p)],`$ (41)
$`\rho _m(r,r^{^{}})`$ $`=`$ $`\varphi _m^{}(r)\varphi _m(r^{^{}})`$ (42)
$`+`$ $`{\displaystyle \underset{p=\pm ,i=1}{\overset{\mathrm{}}{}}}[x_i^p(r)x_i^p(r^{^{}})f_i^p+y_i^p(r)y_i^p(r^{^{}})(1+f_i^p)],`$ (43)
where $`F_i^p=\frac{1}{exp(\beta E_i^p)1}`$ and $`f_i^p=\frac{1}{exp(\beta e_i^p)1}`$ are the Bose distribution for the quasiparticle excitations with energies $`E_i^p`$ and $`e_i^p`$, respectively. Setting $`r=r^{^{}}`$, eq.(19) follows the resulting particle density.

We need to point out that eqs. (17) and (18) are results of the first step of the numerical calculations. To complete numerical calculations, we should repeat the above procedures until the eigenvalues $`E_j`$ and $`e_j`$ do not depend on position $`r`$. In what follows, we present a variation method to study the excitations at zero temperature. This method was first introduced in Ref.  to study the BEC ground state in the harmonic trap of boson system, and it was generalized in Ref.  to investigate the excited states in BEC. Considering eq.(13) as well as

$$[u_j(r)u_j^{}(r)v_j(r)v_j^{}(r)]𝑑r=1,$$

and

$$[x_j(r)x_j^{}(r)y_j(r)y_j^{}(r)]𝑑r=1,$$

which were derived from the Bose commutation relation (6) we arrive at

$`E_j`$ $`=`$ $`{\displaystyle u_j^{}(r)(\frac{^2}{2M}+\lambda |\varphi _m|^2+2\lambda _a|\varphi _a|^2+V_a(r))u_j𝑑r}`$ (44)
$`+`$ $`{\displaystyle v_j^{}(r)(\frac{^2}{2M}+\lambda |\varphi _m|^2+2\lambda _a|\varphi _a|^2+V_a(r))v_j𝑑r}`$ (45)
$``$ $`{\displaystyle u_j^{}(r)(\lambda _a\varphi _a^{}\varphi _a^{}+2\alpha \varphi _m^{})v_j(r)𝑑r}{\displaystyle v_j^{}(r)(\lambda _a\varphi _a^{}\varphi _a^{}+2\alpha \varphi _m^{})u_j(r)𝑑r},`$ (46)
$`e_j`$ $`=`$ $`{\displaystyle x_j^{}(r)(\frac{^2}{4M}+\epsilon +\lambda |\varphi _a|^2+2\lambda _m|\varphi _a|^2+V_m(r))x_j𝑑r}`$ (48)
$`+`$ $`{\displaystyle y_j^{}(r)(\frac{^2}{4M}+\lambda |\varphi _a|^2+\epsilon +2\lambda _m|\varphi _m|^2+V_m(r))y_j𝑑r}`$ (49)
$``$ $`{\displaystyle x_j^{}(r)\lambda _m\varphi _m^{}\varphi _m^{}y_j(r)𝑑r}{\displaystyle y_j^{}(r)\lambda _m\varphi _m^{}\varphi _m^{}x_j(r)𝑑r}.`$ (50)
For simplicity, we study only the case of the spherical harmonic trap. In this case, we may choose the trial wave functions of the excitation components $`u_j(r),v_j(r)`$,$`x_j(r)`$ and $`y_j(r)`$ in the form of the spherical harmonic oscillator wave function $`\xi _{n_r,l,m}`$ with quantum numbers $`(n_r,l,m)`$:

$`\left(\begin{array}{c}u_j(r)\\ v_j^{}(r)\end{array}\right)`$ $`=`$ $`\left(\begin{array}{c}u\\ v^{}\end{array}\right)\xi _{n_r,l,m}(\omega _{n_rlm},r),`$ (56)
$`\left(\begin{array}{c}x_j(r)\\ y_j^{}(r)\end{array}\right)`$ $`=`$ $`\left(\begin{array}{c}x\\ y^{}\end{array}\right)\xi _{n_r,l,m}(\omega _{n_rlm},r),`$ (61)
where $`\omega _{n_rlm}`$ is an adjustable scaling factor of variation. Eqs (20) and (21) show that $`E_j`$ and $`e_j`$ take a similar form, hence we here discuss branches $`E_j`$ of the excitation spectra in detail. For $`(n_r,l,m)=(0,1,0)`$, we have

$$\xi _{0,1,0}=\alpha _{010}^{3/2}[\frac{8}{3\sqrt{\pi }}]^{1/2}\alpha _{010}re^{\alpha _{010}^2r^2/2}Y_{1,0}(\theta ,\psi ).$$

The excitation spectrum in this case is reduced to

$`E`$ $`=`$ $`E[v,\omega _{010}]=(1+2v^2)[{\displaystyle \frac{5}{4}}\mathrm{}\omega _{010}+{\displaystyle \frac{5}{4}}\mathrm{}{\displaystyle \frac{\omega _a^2}{\omega _{010}}}]`$ (62)
$`+`$ $`\lambda (1+2v^2)N_m\omega _m^{3/2}[{\displaystyle \frac{2M}{\pi \mathrm{}}}]^{3/2}[{\displaystyle \frac{\omega _{010}}{\omega _{010}+2\omega _m}}]^{5/2}`$ (63)
$`+`$ $`[2\lambda _a(1+2v^2)2\lambda _av\sqrt{1+v^2}]N_a\omega _a^{3/2}[{\displaystyle \frac{M}{\pi \mathrm{}}}]^{3/2}[{\displaystyle \frac{\omega _{010}}{\omega _{010}+\omega _a}}]^{5/2}`$ (64)
$``$ $`4\alpha v\sqrt{1+v^2}[{\displaystyle \frac{\omega _{010}}{\omega _{010}+\omega _m}}]^{5/2}N_m^{1/2}\omega _m^{3/4}[{\displaystyle \frac{2M}{\pi \mathrm{}}}]^{3/4},`$ (65)
where $`\alpha _{010}^2=\frac{M\omega _{010}}{\mathrm{}}.`$Similarly, for $`(n_r,l,m)=(1,0,0),`$ we have

$$\xi _{1,0,0}=\alpha _{100}^{3/2}[\frac{8}{3\sqrt{\pi }}]^{1/2}(\frac{3}{2}\alpha _{100}^2r^2)re^{\alpha _{100}^2r^2/2}Y_{0,0}(\theta ,\psi ).$$

And

$`E`$ $`=`$ $`E[v,\omega _{100}]=(1+2v^2)[{\displaystyle \frac{7}{4}}\mathrm{}\omega _{100}+{\displaystyle \frac{7}{4}}\mathrm{}{\displaystyle \frac{\omega _a^2}{\omega _{100}}}]`$ (66)
$`+`$ $`\lambda (1+2v^2)N_m\omega _m^{3/2}[{\displaystyle \frac{2M}{\pi \mathrm{}}}]^{3/2}f(\omega _{100},2\omega _m)`$ (67)
$`+`$ $`[2\lambda _a(1+2v^2)2\lambda _av\sqrt{1+v^2}]N_a\omega _a^{3/2}[{\displaystyle \frac{M}{\pi \mathrm{}}}]^{3/2}f(\omega _{100},\omega _a)`$ (68)
$``$ $`4\alpha v\sqrt{1+v^2}f(\omega _{100},\omega _m)N_m^{1/2}\omega _m^{3/4}[{\displaystyle \frac{2M}{\pi \mathrm{}}}]^{3/4},`$ (69)
where

$$f(x,y)=\frac{3}{2}(\frac{x}{x+y})^{3/2}3(\frac{x}{x+y})^{5/2}+\frac{5}{2}(\frac{x}{x+y})^{7/2}.$$

Minimizing the energies of eqs (23) and (24) with respect to the variation parameters $`v`$, $`\omega _{010}`$ and $`\omega _{100}`$, we can determine the excitation spectrum for the mode $`(0,1,0)`$ and $`(1,0,0)`$. The numerical results are illustrated in fig.1 and fig.2. The dashed lines in figures show the excitation spectrum in atom BEC, i.e., $`\alpha =\lambda =0`$. In contrast, the solid line are those of hybrid atomic/molecular condensates near Feshbach resonance. From fig.1 and fig.2 we see that while the excitation frequency for modes $`(0,1,0)`$ increases due to the Feshbach resonance effect, the excitation frequency for the mode $`(1,0,0)`$ decreases. We would like to point out that the numerical results presented here depend on the coupling constant as well as the parameter $`\alpha `$. In Fig.1 and Fig.2, we let $`\alpha =5\lambda _a`$, and $`\lambda _a=0.1`$ (arbitrary units). The other parameters in Fig.1 and Fig.2 are $`\omega _m=1.4\omega _a=7500Hz,`$ $`N_a=N_m=10^6`$.

For clarity, we illustrate the above somewhat formal discussion by considering the binary atom system for a uniform system ($`V_{a(m)}(r)0`$), in this case $`H_{FR}`$ gives a resonant contribution to the atom-atom interaction strength $`a_a`$: $`a_{eff}=a_0(1+\frac{\mathrm{\Delta }}{B_0B})`$, where $`a_0`$ is the off-resonant scattering length, and $`\mathrm{\Delta }`$ characterizes the width of the resonance. For small $`p`$, these excitations are phonons, and their energy tends to zero with $`p`$. Hence,

$$\mu _a=\lambda |\varphi _m|^2+\lambda _a|\varphi _a|^22\alpha \varphi _m^{},$$
(70)
which leads to

$$E_j^2=E^2(p)=(\frac{\mathrm{}^2}{2m})^2p^2(p^2+16\pi na_{eff}).$$
(71)
For a uniform dilute Bose gas with negative scattering length $`a_{eff}`$, eq.(26) implys an instability of those modes with $`p^216\pi n|a_{eff}|`$. For a gas in a trap, however, the wavenumber cannot be arbitrarily small, and the minimum value is of order $`p_{min}\pi /R_0`$( $`R_0`$ is the mean size of the ground state). Hence the system can remain stable if $`\frac{\pi ^2}{R_0^2}16\pi n|a_{eff}|.`$ Since the density is of order $`nN/R_0^2`$, this means that the critical number of the system is

$$N_0\frac{\pi }{16}\frac{R_0}{|a_{eff}|}.$$
(72)
For a positive scatering length $`a_{eff}`$, however, there are not any constraints in $`N`$. The Bogoliubov quasiparticle theory shows that the condensate atoms $`N_0`$ depends on the scattering length and satisfies (for $`(a_{eff}\frac{N}{V})^{\frac{1}{3}}<<1`$).

$$N_0=N(1\frac{8}{3}\sqrt{\frac{Na_{eff}^3}{\pi V}}).$$
(73)
The numerical results of eqs.(27) and (28) are illustrated in Fig.3, which shows the atom number $`N_0`$ vs. external magnetic field $`B`$. The parameters in Fig.3 are $`N/V=N/R^2=10^{15}/cm^3`$, $`\mathrm{\Delta }=0.01mT`$.

To sum up, we have derived a set of four coupled equations of the atomic and molecular excitations within standard Hartree-Fock-Bogoliubov approximation. As shown in eqs. (9) and (13), the $`\alpha `$ terms describing the process that converts atoms into molecules play an important role in atomic/molecular Bose-Einstein condensation. In particular, two low excitation spectrum have been given at zero temperature, which show that the interaction between the hybrid atomic/molecular BEC increase one excitation mode, while they decrease another excitation mode. The mode (0,1,0) comes from the density fluctuation of the condensate like vibrating oscillation, in this sense that the mode (0,1,0) increases near the Feshbach resonance indicates the presence of the Feshbach resonance enhance the density fluctuation like vibrating oscillation in atomic/molecular condensation system, whereas the breath mode(like breathing oscillation) (1,0,0) decrease near the Feshbach resonance. Within the two-body collision regime, we show the atom number remained in BEC vs. the external magnetic field $`B`$, the result is in good agreement with the recent experiment. This work removes from consideration of the case at resonance, since at resonance the Bogoliubov approximation is not available( at resonance, there are few atoms in condensate). The contributions of the noncondensate atoms(molecules) to the excitation spectrum is also ignored (see eq.(9)). These need further investigations.

Figure Captions

Fig.1: Excitation spectrum of Mode $`(0,1,0)`$ vs. number of atoms. Dotted and dashed line indicate those with and without Feshbach resonance, respectively.
Fig.2:Same as fig.1. But for mode $`(1,0,0)`$.
Fig.3:The number of atoms in condensate vs. magnetic field $`B`$.