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# Heterogeneous condensation in dense media

## 1 Profile around the solitary droplet

Due to the external influence in the initial moment of time one can observe in the system the homogeneous mother metastable phase with the particle number density $`n`$ which is equal to some value $`n_0`$. All heterogeneous centers are distributed rather homogeneously in space with the number density $`\eta _{tot}`$.

The process of condensation can begin only when $`n_0`$ is greater than the molecule number density $`n_{\mathrm{}}`$ in the vapor saturated over the plane liquid. The power of metastability of vapor will be characterized by the value of a supersaturation $`\zeta `$ defined as

$$\zeta =\frac{n}{n_{\mathrm{}}}1$$

The initial value of the supersaturation will be marked by $`\zeta _0`$.

Practically immediately around every center there will be formed an equilibrium embryo which has $`\nu _e`$ molecules of the condensing substance. The value of $`\nu _e`$ is relatively small555In comparison with the characteristic number of molecules inside the droplet during the nucleation period. and there is no need to consider the density profile around the equilibrium embryos666In fact it will disappear rather fast. This leads to the slight variation of the equilibrium embryo characteristics. This variation will act on the gap. But the final relaxation will be rather rapid..

The number of the equilibrium embryos in the unit volume777The system of a unit volume will be considered. will be equal to $`\eta _{tot}`$. During the condensation process the number of the equilibrium embryos $`\eta `$ will be decreased due to the exhaustion of the free heterogeneous centers

$$\eta =\eta _{tot}N$$

where $`N`$ is number of the supercritical embryos which will be called as the droplets.

The last equation illustrates the main specific feature in kinetics of heterogeneous condensation. Despite the simple form of the last relation the effect is very complicate because $`N`$ depends on time in a very complicate manner.

The effects of the density profile will be essential also for $`N`$ and one can not directly apply the results of . One has to determine the effect of the influence on $`N`$ even for the density profile of the solitary droplet.

We shall call an approach where the law of embryos growth is found from continuous model but there is no account of the profile around the droplets as the ”Additive approach” (AA).

Then one can formulate the evident

Statement 1

The duration of the nucleation period888The period of nucleation is the period of the relatively intensive formation of the droplets. It can be proven that the end of this period is well defined due to the cut-off of the intensity of the droplets formation. and the characteristic sizes of the droplets at the end of nucleation period are greater than those calculated in AA

Really, the existence of the density profile means that the part of substance is going to be consumed from the regions where there is already no droplets formation. This substance is consumed from the gap instead of unexhausted regions as it is done in AA.

Then having repeated all constructions999In  the AA was formulated for external conditions of dynamic type. For the situation of decay the required hierarchical inequalities can be proven by the same way. One can note that in  there is no special reference on the type of condition when the required estimates are proven. from  one can see101010The barrier character of nucleation is required here. It means that the magnitude of the activation barrier height has the same order as the free energy of the homogeneous critical embryos (may be it is $`4`$ or $`3`$ times smaller).

Statement 2

The characteristic size of the droplets at the end of the nucleation period is many times greater than the size of the critical embryo. The main role in vapor consumption is played by the supercritical embryos.

and

Statement 3

The characteristic time of the nucleation period duration is many times greater than the time of relaxation to the stationary state in the nearcritical region. Then one can use the stationary rate of nucleation as the intensity of the droplets formation in every current moment of time.

Due to the statement 2 one has to investigate the profile around a growing droplet. The problem is whether one has to consider the interference of profiles around different droplets.

To solve this problem one has to use the small parameter of the theory. Due to the statement 3 the rate of nucleation is equal to the stationary one. It can be taken from

$$I_s=Z\eta exp(\mathrm{\Delta }F)$$

where $`\mathrm{\Delta }F`$ is the height of activation barrier (taken in thermal units), $`\eta `$ is the number of free (unoccupied by the supercritical embryos) heterogeneous centers, $`Z`$ is Zeldowitch factor. Zeldowitch factor is the smooth function of the supersaturation which is given by

$$Z=\frac{W}{\pi ^{1/2}\mathrm{\Delta }\nu _e\mathrm{\Delta }\nu _c}$$

where $`W`$ is kinetic factor, $`\mathrm{\Delta }\nu _c`$ is the halfwidht of the nearcritical region, $`\mathrm{\Delta }\nu _e`$ is the width of the equilibrium region.

Due to the rather small size of the critical embryo it is reasonable to use the free molecular regime of the substance exchange111111As long as the characteristic size of the droplet during the nucleation is many times greater that the critical size the diffusion regime of growth for the characteristic droplets is quite reasonable.. Namely, in this regime an expression for the nucleation rate is well based. One has also to note that the critical embryo is in equilibrium (unstable one) with the metastable phase which implies no profiles of vapor density and regime of the substance exchange is the free molecular one.

Under the free molecular regime $`W`$ can be calculated as

$$W=3\frac{\zeta +1}{\tau }\nu _c^{2/3}\alpha $$

where $`\nu _c`$ is the number of molecules inside the critical embryo, $`\alpha `$ is the condensation coefficient,

$$\tau =12[(36\pi v_l^2)^{1/3}n_{\mathrm{}}v_T]^1$$

is the characteristic time, $`v_l`$ is a volume per one molecule in a liquid phase, $`v_T`$ is the mean thermal velocity of a molecule.

The value of $`\mathrm{\Delta }\nu _c`$ is the halfwidth of the nearcritical region and it can be calculated as

$$\mathrm{\Delta }\nu _c=\underset{\nu (\nu _c+\nu _e)/2}{}\mathrm{exp}(F_c+F_\nu )\pi ^{1/2}$$

where $`\nu `$ is the number of the molecules inside the embryo, $`F_\nu `$ is the free energy of the embryo of $`\nu `$ molecules, $`F_c`$ is the free energy of the critical embryo. In continuous approximation it can be calculated as121212Ordinary $`\mathrm{\Delta }\nu _e`$ is smaller than $`\mathrm{\Delta }\nu _c`$ and an explicit summation for $`\mathrm{\Delta }\nu _c`$ is quite reasonable.

$$\mathrm{\Delta }\nu _c=|\frac{2}{\frac{\delta ^2F}{\delta \nu ^2}}|_{\nu =\nu _c}|^{1/2}$$

The value of $`\mathrm{\Delta }\nu _e`$ can be calculated as

$$\mathrm{\Delta }\nu _e=\underset{\nu (\nu _e+\nu _c)/2}{}\mathrm{exp}(F_\nu +F_e)$$

where $`F_e`$ is the free energy of the equilibrium embryo.

Both $`\mathrm{\Delta }\nu _c`$ and $`\mathrm{\Delta }\nu _e`$ are rather smooth functions of the supersaturation.

One can see that $`I_s`$ is a very sharp function of the supersaturation. It means that the relatively small fall of the supersaturation leads to the interruption of the droplets formation.

At least for all $`\zeta >\zeta _0/2`$ one can show that $`d^2\zeta /dt^2>0`$ and the is no long tail of a size spectrum with a small intensity. It means that the interruption of the droplets formation leads to the interruption of the nucleation process. So, the relative fall of the supersaturation during the nucleation process is small. One can come to the following statement

Statement 4

During the nucleation period the relative variation of supersaturation is small.

The last statement shows that there is no need to consider the interference of profiles in order to change the rate of droplets growth.

On the base of mentioned expressions and the smallness of the relative fall of supersaturation one can see the validity of the following approximation

$$I_s(\zeta )=I_s(\zeta _0)\mathrm{exp}(\mathrm{\Delta }F(\zeta _0)\mathrm{\Delta }F(\zeta ))$$

for the nucleation period.

Moreover one can linearize the height of the activation barrier over the supersaturation and get

$$I_s(\zeta )=I_s(\zeta _0)\mathrm{exp}(\frac{d\mathrm{\Delta }F(\zeta )}{d\zeta }|_{\zeta =\zeta _0}(\zeta \zeta _0))$$
(1)
The validity of the last approximation depends on the concrete type of heterogeneous centers but for the majority of the heterogeneous centers types the last approximation is valid. For example, this validity can be directly proven for ions.

One can explicitly calculate the derivative in the last expression131313Here we assume the vapor to be an ideal gas and suppose the possibility to present the free energy of critical and equilibrium embryos as an analytical function of an inverse embryo radius.

$$\frac{d\mathrm{\Delta }F}{d\zeta }=\frac{1}{\zeta +1}(\nu _c\nu _e)$$

The smooth character of the last expression shows the validity of (1) one more time.

Then (1) can be rewritten as

$$I_s(\zeta )=I_s(\zeta _0)\mathrm{exp}(\mathrm{\Gamma }\frac{\zeta \zeta _0}{\zeta _0})$$
(2)
where

$$\mathrm{\Gamma }=\zeta _0\frac{d\mathrm{\Delta }F}{d\zeta }|_{\zeta =\zeta _0}=\frac{\zeta _0}{\zeta _0+1}(\nu _c(\zeta _0)\nu _e(\zeta _0))$$

As far as the value of $`\nu _c`$ in going in the presented theory to infinity the value of $`\mathrm{\Gamma }`$ is also going to $`\mathrm{}`$. The real value of $`\mathrm{\Gamma }`$ is very big. Certainly, one can consider the possibility of compensation between $`\nu _c`$ and $`\nu _e`$ in the expression for $`\mathrm{\Gamma }`$. Then one has to mention thatdue to the barrier character of nucleation at least $`\nu _c\nu _e\mathrm{\Delta }\nu _c`$. Having estimated $`\mathrm{\Delta }\nu _c`$ by the homogeneous value $`\mathrm{\Delta }\nu _c\nu _c^{2/3}`$ one can see that $`\mathrm{\Gamma }1`$ in any case.

The small value of $`\mathrm{\Gamma }^1`$ will be very important in further constructions.

We see that essential dependence over the supersaturation occurs through the height of activation barrier. It allows to give the interpretation of the stationary rate of nucleation as the probability for the given embryo to overcome the activation barrier. After the interpretation of $`I_s`$ as the probability we can apply it to the arbitrary spatial point of spatially unhomogeneous system. To use this interpretation the natural requirement is the weak unhomogenity of the system. Namely, the volume of the regions where

$$\frac{\zeta (r)\zeta (r+\sqrt{4Dt_s})}{\zeta (r)}\mathrm{\Gamma }^1$$

is violated has to be relatively small.

Here $`D`$ is the diffusion coefficient, $`t_s`$ is the time of relaxation in the nearcritical region which can be estimated according to Zeldowitch

$$t_s\frac{\mathrm{\Delta }\nu _c^2}{W}$$

One can use instead of $`t_s`$ the time $`Z^1`$ which can be interpreted as the mean time to overcome the nearcritical region.

Both these estimates are observed. Actually we need them only for those regions where the intensity of the droplets formation isn’t too small in comparison with initial intensity. Certainly, the required property is observed there.

Now we have to turn to the rate of embryos growth. According to the Statement 2 the characteristic size of droplets is rather big. Then it is more reasonable to use the diffusion regime of droplets growth. Under the intermediate Knudsen numbers one has to use an interpolation law for the rate of embryos growth (for example, see ). It will be important that all expressions for the embryos growth lead to the avalanche character of the substance consumption.

The avalanche character of the substance consumption means that the quantity of substance accumulated by a droplet strongly increases in time. The most evident manifestation of the avalanche consumption can be seen in the free molecular regime of the substance consumption. The most ”weak” effect of the avalanche consumption can be seen under the diffusion regime of the substance consumption.

The force of the iterations convergence in  is based on this property. The property of avalanche consumption will be extremely important in the further constructions also. That’s why we take the diffusion regime to have the worst situation and to grasp errors in all possible cases.

In the diffusion regime of the vapor consumption the law of growth for a droplet (i.e. for the supercritical embryo) can be written in the following way

$$\frac{d\nu }{dt}=\kappa \zeta \nu ^{1/3}$$

where

$$\kappa =(\frac{2}{3})^{1/3}4\pi n_{\mathrm{}}D(\frac{v_l}{2\pi })^{1/3}$$

is some constant.

The last expression is written in stationary approximation. The non-stationary effects were investigated in many publications in details and they are rather small ones.

One can see that the rate of the droplet growth is proportional to $`\zeta `$. So, the rate of growth can be essentially changed only by the essential relative variation of $`\zeta `$. Then according to Statement 4 one can see that

Statement 5

The rate of droplets growth during the nucleation period can be approximated as a constant one.

The last statement is extremely important because is allows to analyze the profile of the density initiated by a solitary droplet. Now this case will be considered.

The approximately constant value of the supersaturation allows to integrate the law of growth and get

$$\nu (t)=\gamma t^{3/2}$$

where

$$\gamma =(4\pi )^{3/2}(\frac{3v_l}{4\pi })^{1/2}(\frac{2\zeta n_{\mathrm{}}D}{3})^{3/2}$$

and $`t`$ is the duration of the irreversible growth for the given droplet.

Consider the spherical system of coordinates with a center in the center of droplet. Diffusion equation will be written as

$$\frac{n}{t}=D\mathrm{\Delta }n$$

where $`\mathrm{\Delta }`$ is the Laplace operator. Diffusion coefficient $`D`$ is supposed to be approximately constant (there is a lot of a passive gas and the density of a gas mixture is approximately constant).

The boundary conditions are the following

$$n|_{r=\mathrm{}}=n(\mathrm{})$$

$$n|_{r=R_d}=n_{\mathrm{}}$$

where $`R_d`$ is the radius of a droplet. The values $`n_{\mathrm{}}`$ and $`n(\mathrm{})`$ are known parameters. The variable $`r`$ is the distance until the center of the embryo.

The stationary approximation is suitable for the rate of droplets growth. The errors are analyzed in  and they are small. But the stationary solution can not give any reasonable result for the density far from the droplet. Really, the stationary solution is the following

$$n(r)=n(\mathrm{})\frac{R_d}{r}(n(\mathrm{})n_{\mathrm{}})$$
(3)
and has a very long tail. This tail leads to the infinite value of

$$G=_0^{\mathrm{}}4\pi r^2(n(\mathrm{})n(r))𝑑r$$

which has to be the integral excess of the substance. This quantity has to be in the droplet. This contradiction shows that it is absolutely impossible to use the stationary approximation for the density profile around the droplet. One has to introduce another approach.

One can see that if the first boundary condition will be changed by

$$n|_{r=\mathrm{}}=n(\mathrm{})(1\mathrm{\Gamma }^1)$$

then the rate of embryos growth will be changed unessentially. But the level $`n(\mathrm{})(1\mathrm{\Gamma }^1)`$ is the level when the nucleation stops. So, one can see that during the nucleation period there is no interaction between droplets through the change of the growth rate. Certainly, two droplets can appear too close and act one upon another but the probability of such coincidence is too small. That is why one can come to the ”Principle of a separate growth of droplets during the nucleation period”.

Now one has to prove that at the distances $`(5÷10)R_d`$ from the droplet one can observe the quasistationary profile.

One has to note that

$$v_l/v_v1$$
(4)
where $`v_v`$ is the partial molecule volume in a vapor phase. Really, the last ratio is very small (for example, this ratio is $`0.001`$ for water in normal thermodynamic conditions). But contrary to $`\mathrm{\Gamma }^1`$ one can not consider it in all cases as zero.

Now one can introduce a formal parameter $`l`$ which attains big values

$$l1$$

but satisfies the following condition

$$l^2\frac{v_l}{v_v}1$$
(5)
Due to (4) it is possible to do.

In the region $`rlR_d`$ the stationary profile is established after

$$t_h=\frac{l^2R_d^2}{4D}$$

It is necessary to show that

$$s\frac{R_d(t+t_h)R_d(t)}{R_d(t)}1$$

Really,

$$s\frac{dR_d}{dt}\frac{t_h}{R_d}$$

and

$$sl^2\frac{v_l}{v_v}$$

which is a small value according to (5). So, the stationary form of profile in the region $`r<R_dl`$ is proven.

As far as $`\mathrm{\Gamma }1`$ and at least $`\mathrm{\Gamma }l`$ one can see that in the region $`r<lR_d`$ there is no formation of new droplets. Then this region isn’t interesting for the theory and one can only observe the region $`r>lR_d`$.

The previous notation is rather important. Namely this property allows to use the model with a point source. Really, one can consider only the distances greater than $`lR_d`$. But at these distances the droplet can be interpreted as a point.

Certainly, the point approximation of a droplet can not give an expression for the rate of droplets growth because the boundary condition at $`r=R_d`$ is absent. But the rate of growth is already known and can be used directly as a known function of time. Really,

$$\frac{d\nu }{dt}=\lambda t^{1/2}$$

where

$$\lambda =2^{5/2}\pi v_l^{1/2}\zeta ^{3/2}n_{\mathrm{}}^{3/2}D^{3/2}$$

The action of a point source of a vapor consumption can be described in a simple and suitable manner under the Green function formalism. The Green function for the diffusion equation can be written in a following form

$$Gr=\mathrm{\Theta }(t)\frac{\mathrm{exp}(\frac{r^2}{4Dt})}{(4\pi Dt)^{3/2}}$$

Then one can get the density profile by a simple integration

$$n(r)=n(\mathrm{})_0^t\frac{\lambda x^{1/2}}{(4\pi D(tx))^{3/2}}\mathrm{exp}(\frac{r^2}{4D(tx)})𝑑x$$

After evident transformations one can come to

$$\frac{\zeta _0\zeta }{\zeta _0}=\sqrt{\frac{2}{\pi }}\sqrt{\frac{v_l}{v_v}}f(\beta )$$
(6)
where

$$\beta =\frac{r}{\sqrt{4Dt}}$$

and

$$f(\beta )=_\beta ^{\mathrm{}}(\frac{1}{\beta ^2}\frac{1}{x^2})^{1/2}\mathrm{exp}(x^2)𝑑x$$

It is important that the profile dependence on $`t`$ and $`r`$ is now going through $`\beta `$.

Concrete form of $`f(\beta )`$ is drawn in fig. 1. One can get for $`f(\beta )`$ an expression through special functions

$$f(\beta )=\frac{1}{2}\mathrm{\Gamma }(\frac{3}{2})\mathrm{exp}(\beta ^2)\mathrm{\Psi }(\frac{3}{2},\frac{3}{2};\beta ^2)$$

Here $`\mathrm{\Gamma }`$ is the Gamma-function , $`\mathrm{\Psi }`$ is the confluent hypergeometric function.

One can get asymptotes for $`f(\beta )`$ at small and big values of $`\beta `$. At small values

$$f(\beta )\frac{\sqrt{\pi }}{2}\frac{1}{\beta }$$
(7)
which corresponds to the stationary solution (3).

At big values of $`\beta `$ one can come to

$$f(\beta )=\mathrm{exp}(\beta ^2)\frac{1}{2\beta ^3}_0^{\mathrm{}}x^{1/2}\mathrm{exp}(x)𝑑x\frac{\mathrm{exp}(\beta ^2)}{\beta ^3}$$
(8)
One can see that this asymptote radically differs from the stationary solution. Namely this tail behavior ensures the convergence of the integral for $`G`$. Certainly, the Green function formalism ensures a precise value for $`G`$ which is introduced here as an external object.

Now one can turn to construct some approximation for the nucleation rate around the growing droplet.

One can see that according to (2) the behavior of the supersaturation is important when $`\zeta _0\zeta (2÷3)\zeta _0/\mathrm{\Gamma }`$. When $`\zeta _0\zeta (2÷3)\zeta _0/\mathrm{\Gamma }`$ the intensity of the droplets formation is negligibly small. From (1) one can see that

$$I_s(\zeta (r))=I_s(\zeta _0)\mathrm{exp}(\mathrm{\Gamma }\sqrt{\frac{2}{\pi }}\sqrt{\frac{v_l}{v_v}}f(\beta ))$$

Then one can extract a positive parameter

$$\sigma \mathrm{\Gamma }^2\frac{v_l}{v_v}$$

which will be important in further constructions.

Due to $`\mathrm{\Gamma }1`$ one can easily see that

$$\sigma 1$$

The last condition isn’t necessary for further constructions, but it will be rather important for manifestation of profile effects in the nucleation process.

The last condition is also the most doubtful one because $`v_l/v_v1`$ and one has the ration of two big parameters with generally unknown result. It is necessary to stress that condition $`v_l/v_v1`$ isn’t so strong as $`\mathrm{\Gamma }1`$. In frames of thermodynamic description $`\mathrm{\Gamma }1`$ is the main condition necessary to give the thermodynamic description and $`v_l/v_v1`$ is the supplementary condition which isn’t absolutely necessary but slightly simplifies the theory.

In the situation of homogeneous condensation one has the ”hidden contradiction between the thermodynamic description and the relatively intensive nucleation”. Really, as far as in the homogeneous condensation $`\mathrm{\Delta }F=F_c\nu _c^{2/3}`$ the limit $`\nu \mathrm{}`$ means $`\mathrm{\Delta }F\mathrm{}`$ and the rate of nucleation goes to zero. So, there is the contradiction between thermodynamic limit in the critical embryo description and the observable141414Which isn’t too small. rate of nucleation.

In the case of heterogeneous condensation there is no such contradiction if there are some active centers of condensation. Then the height of the activation barrier has no direct connection with a number of molecules inside the critical embryo. For example, the halfwidth of the nearcritical region estimated by a homogeneous value has a value $`\nu ^{2/3}`$ and goes to infinity when $`\nu \mathrm{}`$, but the free energy decreases at the boundary of the nearcritical region only by one thermal unit. So, in certain sense the case of heterogeneous condensation is more preferable for theoretical description.

As a compensation for this advantage one has to note that the Statement 1 and Statement 2 are based on the homogeneous estimate for the activation barrier height. These properties can be violated. But as far as these Statements are based on very strong inequalities one can accept their validity. The influence of nonstationary effects will be analyzed in a separate publication where the complete theory has been constructed.

Now one can analyze the profile of intensity of the droplets formation around the already existing droplet. This nucleation rate profile is a rather sharp function which has a step-like behavior.

To show this we shall introduce two characteristic values of $`\beta `$ ($`\beta _{st}`$ and $`\beta _{fin}`$) by relations

$$f(\beta _{st})=\sqrt{\frac{\pi }{2}}\sqrt{\frac{v_v}{v_l}}\frac{\mathrm{exp}(1/2)}{\mathrm{\Gamma }}$$

$$f(\beta _{fin})=\sqrt{\frac{\pi }{2}}\sqrt{\frac{v_v}{v_l}}\frac{\mathrm{exp}(1/2)}{\mathrm{\Gamma }}$$

In the region $`\beta >\beta _{st}`$ the rate of nucleation practically coincides with the unperturbed value $`I_s(\zeta _0)`$. In the region $`\zeta <\zeta _{fin}`$ the rate of nucleation is negligible in comparison with the unperturbed value, i.e. $`I_s(\zeta (r))I_s(\zeta _0)`$.

In some moment $`t`$ the values $`\beta _{st}`$, $`\beta _{fin}`$ initiate the space distances $`r_{st}`$, $`r_{fin}`$ by the following expressions

$$r_{st}=\beta _{st}\sqrt{4Dt}$$

$$r_{fin}=\beta _{fin}\sqrt{4Dt}$$

For $`\sigma 1`$ one can come to

$$f(\beta _{st})1$$

$$f(\beta _{fin})1$$

and

$$\beta _{st}1$$

$$\beta _{fin}1$$

Then one can use the asymptote (8) and see that

$$\frac{|\beta _{st}\beta _{fin}|}{\beta _{st}+\beta _{fin}}=\frac{1}{4\beta _{st,fin}}1$$

$$\frac{|r_{st}r_{fin}|}{r_{st}+r_{fin}}=\frac{1}{4\beta _{st,fin}}1$$

The real picture of nucleation is going in the time scale. In a fixed space point $`r`$ one can introduce two characteristic times $`t_{st}`$ and $`t_{fin}`$ by expressions

$$t_{st}=\frac{r^2}{4\beta _{st}^2D}$$

$$t_{fin}=\frac{r^2}{4\beta _{fin}^2D}$$

Before $`t_{st}`$ one can not observe any essential deviation of the nucleation rate from the unperturbed value. After $`t_{fin}`$ the rate of nucleation is very small.

One can get for the relative deviation

$$\delta \frac{t_{fin}t_{st}}{t_{st,fin}}$$

the following expression

$$\delta \frac{1}{\beta _{st,fin}}$$

So, the relative deviation is small.

Even in the situation of small $`\sigma `$ one can show with the help of the asymptote (7) that $`\delta `$ is rather small.

The step-like behavior151515This step can take place even for $`\beta >\beta _{st}`$ when $`\sigma 1`$. of intensity profile allows to introduce some characteristic parameter $`\beta _{eff}`$ and consider the region161616At $`\sigma 1`$ the value of $`\beta _{eff}`$ can be greater tan $`\beta st`$ and $`\beta _{fin}`$.

$$\beta <\beta _{eff}$$

as the exhausted region where there is no nucleation more and in the region

$$\beta >\beta _{eff}$$

the rate of nucleation is unperturbed171717In all cases $`\beta _{eff}>\beta _{fin}`$..

One has to choose $`\beta _{eff}`$ carefully. The problem is the possibility of existence of a long tail of a density profile. To grasp the situation of a small values of $`\sigma `$ one has to introduce $`\beta _{eff}`$ in an integral manner.

One can introduce the excess of nucleation rate $`\mathrm{\Delta }I_s`$ by the following formula

$$\mathrm{\Delta }I_s=I_s_0^{\mathrm{}}(1\mathrm{exp}(\frac{\mathrm{\Gamma }(\zeta _0\zeta (r))}{\zeta _0}))4\pi r^2𝑑r$$

when $`I_s`$ is the unperturbed rate of nucleation.

On the base of the last expression one can get the excess of $`N`$ due to the existence of the solitary profile. This value will be marked by $`\mathrm{\Delta }N_{sol}`$ and can be found as

$$\mathrm{\Delta }N_{sol}=I_s_0^t_0^{\mathrm{}}(1\mathrm{exp}(\frac{\mathrm{\Gamma }(\zeta _0\zeta (r))}{\zeta _0}))4\pi r^2𝑑r𝑑t^{}$$

Having used equation (6) one can come to

$$\mathrm{\Delta }I_s=4\pi (4Dt)^{3/2}I_s_0^{\mathrm{}}(1\mathrm{exp}(\mathrm{\Gamma }\sqrt{\frac{2}{\pi }}\sqrt{\frac{v_l}{v_v}}f(\beta )))\beta ^2𝑑\beta $$

Parameter $`\mathrm{\Gamma }\sqrt{\frac{2}{\pi }}\sqrt{\frac{v_l}{v_v}}`$ has a constant value.

The value $`\mathrm{\Delta }N_{sol}`$ can be now found as

$$\mathrm{\Delta }N_{sol}=4\pi (4Dt)^{3/2}I_s_0^t_0^{\mathrm{}}(1\mathrm{exp}(\mathrm{\Gamma }\sqrt{\frac{2}{\pi }}\sqrt{\frac{v_l}{v_v}}f(\beta )))\beta ^2𝑑\beta 𝑑t^{}$$

The step-like approximation of the nucleation profile will lead to

$$\mathrm{\Delta }I_s^0(\beta _{eff})=4\pi (4Dt)^{3/2}I_s_0^{\beta _{eff}}x^2𝑑x$$

The value $`\beta _{eff}`$ has to be determined from

$$\mathrm{\Delta }I_s^0(\beta _{eff})=\mathrm{\Delta }I_s$$

Certainly, the value of $`\beta _{eff}`$ depends of $`\mathrm{\Gamma }\sqrt{\frac{2}{\pi }}\sqrt{\frac{v_l}{v_v}}`$.

The value of $`\beta _{eff}`$ initiates

$$r_{eff}=2\beta _{eff}D^{1/2}t^{1/2}$$

Inside the volume

$$V_{eff}=\frac{4}{3}\pi r_{eff}^3$$

there is no nucleation and outside this volume the rate of nucleation is unperturbed.

Then one can imagine that around every droplet there exists the exhausted region (ER) where there is no nucleation and the unexhausted region (UR) where the nucleation remains unperturbed. The whole space now is divided into two regions.

The volume $`V_{eff}`$ grows in time in the following way

$$V_{eff}=\frac{32}{3}\pi \beta _{eff}^3D^{3/2}t^{3/2}$$

In a free molecular regime $`V_{eff}`$ will grow even faster.

For $`b_{eff}`$ one can get the simple expression

$$\beta _{eff}^3=3_0^{\mathrm{}}(1\mathrm{exp}(\mathrm{\Gamma }\sqrt{\frac{2}{\pi }}\sqrt{\frac{v_l}{v_v}}f(\beta )))\beta ^2𝑑\beta $$

or

$$\beta _{eff}^3=3_0^{\mathrm{}}(1\mathrm{exp}(\sigma ^{1/2}\sqrt{\frac{2}{\pi }}f(\beta )))\beta ^2𝑑\beta $$

For $`\mathrm{\Delta }N_{sol}`$ one can obtain

$$\mathrm{\Delta }N_{sol}=I_s(\zeta _0)_0^t𝑑t^{}V_{eff}=_0^t𝑑t^{}\frac{4}{3}\pi r_{eff}^3$$

One can easy integrate the last expression and get

$$\mathrm{\Delta }N_{sol}=I_s(\zeta _0)\frac{64}{15}\pi \beta _{eff}^3D^{3/2}t^{5/2}$$

One can see that $`\mathrm{\Delta }N_{sol}`$ is growing in time rather rapidly. Namely this property illustrates the feature of the ”avalanche consumption during the first order phase transition” in application to the heterogeneous nucleation.

For those situations where $`\sigma 1`$ one can get

$$\beta _{eff}\beta _{st}\beta _{fin}$$

and $`\beta _{eff}`$ satisfies the simple equation

$$\mathrm{exp}(\beta _{eff}^2)=\beta _{eff}^3\sqrt{\frac{v_v}{v_l}}\sqrt{\frac{\pi }{2}}\frac{1}{\mathrm{\Gamma }}$$

The last equation can be easily solved by iterations as far as $`\beta _{eff}1`$ and $`\mathrm{exp}(\beta ^2)`$ is the most sharp function of the supersaturation.

Earlier when the principle of the separate growth was discussed then the reason of the absence of interaction between droplets was the low probability to appear too close one to another only due to the smallness of such space volume. Now one can see that the growing ER helps to exclude the interference. Really, the essential deviation of the supersaturation from the ideal one can be seen in the region $`r<R_dl`$. It means that the distance between the droplets with an interference must have the order $`2R_dl`$ Then the time distance between the moments of formation of these droplets must be shorter than

$$\mathrm{\Delta }t_{init}(\frac{R_dl}{\beta _{eff}D^{1/2}})^2$$

This time interval is many times shorter than the duration of the nucleation period.

Every droplet forms rather rapidly after formation the ER of such a size which guarantees that the rate of growth of the given droplet can not be perturbed by a vapor consumption by the other droplets.

## 2 Kinetic models of the global evolution

Now one can construct the picture of nucleation in a whole system. The main problem is to take into account the interference of the density profiles. The interference through the rate of growth is absent, but there is a simple overlapping of profiles which leads to the deviation of the total nucleation rate over the volume from those calculated with account of the additive excesses around every droplet.

The overlapping of ER (even when this approximate formalism is used) is very complex and can not be directly taken into account in precise manner. Instead of writing the long expressions which can not be explicitly calculated one can act in another manner: some simple approximate models for kinetics of the nucleation process will be formulated. From these models it will be seen that they estimate the nucleation characteristics from below and from above and lead practically to the similar results. So, it will be shown that the complex details of the ER overlapping has no strong influence on the real characteristics of the phase transition.

At first one can consider the common feature of all models concerning the exhaustion of free heterogeneous centers.

The rate of nucleation $`I`$ depends on time $`t`$ and on spatial point $`r`$ (the last behavior is the most complex). So, it is reasonable to consider the mean (over the space) value of $`I`$ denoting it by $`<I>`$. For $`<I>`$ one can write the following expression

$$=\frac{W_{free}}{W_{tot}}\frac{\eta }{\eta _{tot}}I_0$$
(9)
where $`I_0`$ is the unperturbed rate of nucleation. Here $`W_{free}`$ is the volume of a region where the rate of nucleation is unperturbed, i.e. the UR of the whole system. The value $`W_{tot}`$ is the total volume of the system (it equals to unity and is written only to clarify the consideration).

Then as far as

$$N=_0^t(t^{})𝑑t^{}$$

one can get

$$\eta =\eta _{tot}_0^t(t^{})𝑑t^{}$$

In the differential form the last relation can be written as

$$\frac{d\eta }{dt}=$$

and with the help of (9) it can be rewritten as

$$\frac{d\eta }{dt}=\frac{\eta }{\eta _{tot}}\frac{W_{free}}{W_{tot}}I_0$$

After the integration of the last expression one can come to

$$\eta =\eta _{tot}\mathrm{exp}(_0^t\frac{W_{free}(t^{})}{W_{tot}}\frac{I_0}{\eta _{tot}}𝑑t^{})$$

One has to note that heterogeneous centers aren’t distributed homogeneously with respect to the ER (or UR). Only free heterogeneous centers are distributed homogeneously with respect to ER. This fact has to be also taken into account.

The problem is to determine the value of $`W_{free}`$. In different models it will be determined in different forms.

The model without overlapping.

One can write

$$W_{free}=W_{tot}W_{exh}$$

where $`W_{exh}`$ is the volume where there is no further formation of the droplets. Very approximately one can present it as the sum of ER around all appeared droplets

$$W_{exh}\underset{i}{}V_{eff}$$

(the sum is taken over all already formed droplets). Certainly, the last approximation is rigorous only when there is no overlapping of the ER around different droplets.

Having used an expression for $`V_{eff}`$ one can come to

$$W_{exh}=_0^t𝑑t^{}(t^{})\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{3/2}$$
(10)
Having used an expression for $`<I>`$ one can come to the closed system of nucleation kinetics equations

$$W_{free}=W_{tot}_0^t𝑑t^{}\frac{\eta }{\eta _{tot}}\frac{W_{free}}{W_{tot}}I_0\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{3/2}$$

$$\eta =\eta _{tot}\mathrm{exp}(_0^t\frac{W_{free}(t^{})}{W_{tot}}\frac{I_0}{\eta _{tot}}𝑑t^{})$$
(11)
In the quasihomogeneous limit (when there is no essential exhaustion of centers) this system can be reduced to

$$W_{free}=W_{tot}_0^t𝑑t^{}\frac{W_{free}}{W_{tot}}I_0\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{3/2}$$

which can be written after the evident renormalization $`tat,t^{}at^{}`$ where $`a=(I_0\frac{32}{3}\pi \beta _{eff}^3D^{3/2})^{2/5}`$ in the universal form

$$W_{free}=1_0^t𝑑t^{}W_{free}(tt^{})^{3/2}$$

One has to note that in the general case the system of nucleation equations can be solved with the help of methods developed in . At first one can solve the quasihomogeneous equation (it the Volterra equation with a rather simple kernel which allows to apply the Laplace transformation to solve it) and then on the base of quasihomogeneous equation one can find the final rather precise expression using the second equation as a formula for $`\eta `$.

Another variant is to solve numerically the universal equation for $`W_{freehom}`$:

$$W_{freehom}=1_0^t𝑑t^{}W_{freehom}(tt^{})^{3/2}$$

Then one has the universal function $`W_{freehom}`$. Then one can find $`\eta `$ as

$$\eta =\eta _{tot}\mathrm{exp}(a^1_0^t\frac{W_{freehom}(t^{})}{W_{tot}}\frac{I_0}{\eta _{tot}}𝑑t^{})$$

The last expression leads to the formula for $`<I>`$ as:

$$=\frac{W_{freehom}}{W_{tot}}\mathrm{exp}(a^1_0^t\frac{W_{freehom}(t^{})}{W_{tot}}\frac{I_0}{\eta _{tot}}𝑑t^{}I_0)$$

The justification of such approach is analogous to . The physical reason is very simple: when there is no exhaustion of heterogeneous centers then the solution is found precisely, when there is an essential exhaustion of centers there is no need to know $`W_{free}`$ with a high precision because the converging force of the operator of the right hand of the second equation in the nucleation equations system is extremely high.

Now we shall take into account the overlapping. It can be done rather approximately.

The model with chaotic overlapping

The matter of discussion is the correct expression for $`W_{free}`$ which can not be got absolutely precisely. Now the more reasonable expression for $`W_{free}`$ will be presented. Certainly, this will lead to a more complicate equation which will be more difficult to solve.

One can use the differential approach to write the expression for $`W_{free}`$. Having written the evident relation

$$\frac{dW_{free}}{dt}=\frac{dW_{exh}}{dt}$$

one has to invent an approximation for $`dW_{exh}/dt`$. Here the following approximation

$$\frac{dW_{exh}}{dt}\frac{d_iV_{eff}}{dt}\frac{W_{free}}{W_{tot}}$$

(the sum is taken over all droplets) will be used. It corresponds to the following approach: The probability of the absence of overlapping of the new parts of ER around the given droplet with other ER is proportional to the free volume of the system.

The last supposition seems to be rather reasonable.

The value $`d_iV_{eff}/dt`$ can be rewritten as

$$\frac{d_iV_{eff}}{dt}=\underset{i}{}\frac{dV_{eff}}{dt}$$

The last value can be easily expressed through $`<I>`$ as

$$\underset{i}{}\frac{dV_{eff}}{dt}=\frac{3}{2}_0^t𝑑t^{}(t^{})\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{1/2}$$
(12)
due to (10).

Then

$$\frac{dW_{exh}}{dt}=\frac{3}{2}_0^t(t^{})\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{1/2}𝑑t^{}W_{free}(t)$$

and

$$\frac{dW_{free}}{dt}=\frac{3}{2}_0^t(t^{})\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{1/2}𝑑t^{}W_{free}(t)$$

Having used an expression for $`<I>`$ one can come to

$$\frac{dW_{free}}{dt}=\frac{3}{2}_0^t\frac{W_{free}}{W_{tot}}I_0\frac{\eta }{\eta _{tot}}\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{1/2}𝑑t^{}W_{free}(t)$$

Together with (11) the last equation forms the closed system of the nucleation equations in the second model.

The previous equation can be integrated which gives

$$\mathrm{ln}W_{free}=_0^t\frac{W_{free}(t^{})}{W_{tot}}I_0\frac{\eta (t^{})}{\eta _{tot}}\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{3/2}𝑑t^{}+const$$

Due to the initial conditions the $`const`$ is equal to zero. Having introduced the function $`F=\mathrm{ln}W_{free}`$ one can get for $`F`$ the following system of equations

$$F(t)=_0^t\mathrm{exp}(F(t^{}))I_0\frac{\eta (t^{})}{\eta _{tot}}\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{3/2}𝑑t^{}$$

$$\eta =\eta _{tot}\mathrm{exp}(_0^t\mathrm{exp}(F(t^{}))\frac{I_0}{\eta _{tot}}𝑑t^{})$$

One can see that the system of condensation equations is identical to the system of nucleation equations in AA. It was completely analyzed in . Certainly, the parameters in the system will be another.

The last system can be rewritten after the evident renormalization as

$$F(t)=_0^t\mathrm{exp}(F(t^{}))(tt^{})^{3/2}\theta (t^{})𝑑t^{}\widehat{F}(F,\theta )$$

$$\theta (t)=exp[A_0^t\mathrm{exp}(F(t^{}))𝑑t^{}]\widehat{\theta }(F)$$

where $`\theta (t)=\eta (t)/\eta _{tot}`$ and $`A`$ is some known parameter.

This system can be solved by iterations defined as

$$F_{i+1}=\widehat{F}(F_i,\theta _i)$$

$$\theta _{i+1}=\widehat{\theta }(F_i)$$

with $`F_0=0`$, $`\theta _0=1`$.

For $`F_i`$, $`\theta _i`$ one can get the chains of inequalities

$$F_0<F_2..<F_{2i}<\mathrm{}<F<\mathrm{}<F_{2i+1}<\mathrm{}<F_3<F_1$$

$$\theta _1<\theta _3<\mathrm{}<\theta _{2i+1}<\mathrm{}<\theta <\mathrm{}<\theta _{2i}<\mathrm{}<\theta _2<\theta _0$$

Then one can estimate errors in $`F_i`$, $`\theta _i`$.

One can use also another methods analogous to those described in .

The similarity of the the condensation equations in AA and in the second model is extremely important for the transition towards collective character of vapor consumption which is analyzed in .

The physical ground of the considered model is the chaotic overlapping of ER. Namely, the chaotic overlapping lies in the base of approximation used here. But due to the spherical form of every ER the overlapping isn’t absolutely chaotic.

What can be done in such a situation? In the next model we shall show that concrete type of overlapping isn’t very important.

To finish with the second model we shall show the same method of its solution as that of the first model.

One can also formulate the quasihomogeneous equation as the following one

$$F_{hom}(t)=_0^t\mathrm{exp}(F_{hom}(t^{}))I_0\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{3/2}𝑑t^{}$$

Then $`\eta `$ can be approximately found as

$$\eta =\eta _{tot}\mathrm{exp}(_0^t\mathrm{exp}(F_{hom}(t^{}))\frac{I_0}{\eta _{tot}}dt^{}$$

The quasihomogeneous equation can be renormalized. After renormalization $`zat`$, $`t^{}at^{}`$ where

$$a=(I_0\frac{32}{3}\pi \beta _{eff}^3D^{3/2})^{2/5}$$

one can transform the quasihomogeneous equation into the universal form

$$\mathrm{ln}W_{freehom}(t)=_0^tW_{freehom}(t^{})(tt^{})^{3/2}𝑑t^{}$$

The model with the formation of droplets inside the ER

The third model will show that the role of overlapping isn’t so essential as it can be imagined from the first point of view.

Suppose that the new droplets can appear also in the ER of the already existed droplets. Then instead of (12) one has to use

$$\underset{i}{}\frac{dV_{eff}}{dt}=\frac{3}{2}_0^t𝑑t^{}I_0\frac{\eta (t^{})}{\eta _{tot}}\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{1/2}$$

Then

$$\frac{dW_{exh}}{dt}=\frac{3}{2}_0^t\frac{\eta (t^{})}{\eta _{tot}}I_0\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{1/2}𝑑t^{}W_{free}(t)$$

and

$$\frac{dW_{free}}{dt}=\frac{3}{2}_0^tI_0\frac{\eta (t^{})}{\eta _{tot}}\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{1/2}𝑑t^{}W_{free}(t)$$

Together with (11) the last equation forms the closed system of the nucleation equations in the third model.

The substance balance equation of the system can be integrated which gives

$$\mathrm{ln}W_{free}=_0^tI_0\frac{\eta (t^{})}{\eta _{tot}}\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{3/2}𝑑t^{}+const$$

Due to the initial conditions the $`const`$ is equal to zero. Having introduced the function $`F=\mathrm{ln}W_{free}`$ one can get for $`F`$ the following system of equations

$$F(t)=_0^tI_0\frac{\eta (t^{})}{\eta _{tot}}\frac{32}{3}\pi \beta _{eff}^3D^{3/2}(tt^{})^{3/2}𝑑t^{}$$

$$\eta =\eta _{tot}\mathrm{exp}(_0^t\mathrm{exp}(F(t^{}))\frac{I_0}{\eta _{tot}}𝑑t^{})$$

This system corresponds to the first iteration in the iteration solution of the second model by the method of iterations of a type ”a” described in . It is also described here. But for $`\eta `$ the whole set of iterations has been taken (see details in ).

One can slightly modify the model and suppose that in the expression for $`\eta `$ one can use the same approximation for $`<I>`$ as in equation for $`W_{free}`$. Then the system of equation will precisely correspond to the first iteration in the iteration solution in .

Actually one needn’t to analyze these models in details following  but has only to note that all these solutions are practically similar. One can see the solution of the third model (both variants) after the same renormalizations as in the second model.

Now one has to explain why the third model is rather accurate. One can do it only with the help of results obtained in .

In  it was noted that when the power of the kernel $`(tt^{})`$ is rather big then the solution of the quasihomogeneous equation weakly depends on concrete value of a power.

Another important notation shows that when the power of $`(tt^{})`$ is extremely high then the ER of the given (first) droplet formed inside the ER of another (second) droplet practically can not go outside the ER of that (second) droplet. Then the third model is absolute adequate in this situation. The same feature can be seen directly from the iteration procedure results.

Having combined these two notations one can see that on one hand the second model is close to the situation with great power of the kernel and in the situation with the big kernel the third model is suitable.

Now it is possible to explain why the overlapping isn’t so important as it can be imagined. Really, as far as the power of kernel is big and one can observe the avalanche consumption one can see the following qualitative picture

* Practically during all period of nucleation the total ER is small and there is no problem of overlapping.
* At the end of the nucleation period the total ER is going to occupy the essential part of the volume and a few moments late it occupies all the volume of the system. This process is very rapid. It stops the nucleation.

This picture shows that there is no strong influence of the overlapping on the nucleation process (except the cut-off).

As the result the nucleation description is completed. One can use both the second and the third model to get the nucleation description. How to solve these equations is also described here.

The method of universal solution

The main idea of the theory presented in  was to consider the quasihomogeneous equation, to get the universal solution and then on the base of this solution to calculate the number of free heterogeneous centers. As the result one can get an expression for $`<I>`$ and can calculate the total number of droplets appeared on the nucleation process.

Here one can follow the same idea. But one can make this idea more deep. One needn’t to formulate the universal quasihomogeneous equation. Instead of equation one can formulate the universal model.

The model will be the following

* -the rate of nucleation $`<I>`$ can be found from

$$=I_0\frac{W_{free}}{W_{tot}}\frac{\eta }{\eta _{tot}}$$
* \- with intensity $`I_0`$ the droplet appears in the arbitrary point of the system which belongs to the free volume.
* -the value $`W_{free}`$ can be found by exclusion of all ER around the already existing droplets.
* \- if the point is occupied by the ER of any droplet then the droplet can not be formed.
* \- the size $`r_{eff}`$ of ER grows in time according to

$$r_{eff}=2\beta _{eff}D^{1/2}t^{1/2}$$
* -the initial condition is the absence of droplets and random distribution of centers.

With the proper renormalization of time $`t`$ and size $`r`$ one can cancel all coefficients. Then this process will be the universal one and as the result $`W_{free}`$ is the universal function of time. Then one can directly apply (11) and get the number of free heterogeneous centers (after the proper renormalization)181818This is quasihomogeneous approach method.

The modification for the dynamic conditions requires to put instead of $`I_0`$ the value $`I_0exp(ct)`$ with some parameter $`c`$ determined by external conditions and to change the lower limit $`0`$ of integration to $`\mathrm{}`$ .

The main constructions of the theory will be absolutely the same but the forms of characteristic curves changes radically.

## 3 Numerical results

Numerical simulation in the nucleation kinetics plays at least two important roles. The first role is the standard comparison with the approximate models to observe their quality. The second one is more specific and it is concerned with some universal dependencies in the nucleation kinetics.

In the AA to the nucleation kinetics it was shown that the adequate approach can be presented on the base of the quasihomogeneous solution . Despite the dynamic conditions considered in  one can observe this property in the situation of the metastable phase decay also. Recall the reasons for such approach.

The formal reason is the careful analysis of the iteration procedure proposed in . Really, the final result for the total number of droplets appeared in the nucleation process is given by the second iteration (see iterations of type ”a” in ) for the relative number of free heterogeneous centers. This iteration is based only on the first iteration for the supersaturation. The value of supersaturation there is calculated without any account of the heterogeneous centers exhaustion. So, one can see that the final result can be obtained on the base of the supersaturation in the quasihomogeneous approximation. This approximation can be more sophisticated than the first iteration. Namely this approach was used in  where the precise quasihomogeneous universal solution was chosen as base for the final results.

The physical reason of such behavior is rather simple. The main role in the vapor consumption belongs to the droplets of relatively large sizes. We have already marked this fact. But moreover, due to the avalanche character of the vapor consumption the main role in vapor consumption is played by the relatively large droplets which are formed in the first moments of time of the nucleation period. When the effect of the centers exhaustion is essential already in the first moments of nucleation period191919More precisely one can define these ”first moments of time” as $`2/5`$ of the nucleation period duration (under the free molecular regime it is $`1/4`$ of the nucleation period duration). The reason for concrete value can come from the iteration procedure. then at the end of nucleation period already all centers will be exhausted. Then the result is evident - all centers are the centers of droplets. Due to the high force of convergence in this situation this result can be gotten under the rather arbitrary behavior of supersaturation (even including the quasihomogeneous case). In the opposite case the exhaustion of heterogeneous centers during the first moments of the nucleation period isn’t essential and one can get the quasihomogeneous behavior of supersaturation.

This effect will be called as the ”approximate separation of the heterogeneous and homogeneous problems”. It is based only on the avalanche consumption of the metastable phase. So, there are no objections to see this effect also in the situation with the density profiles. Then it is extremely important to get solution in the quasihomogeneous situation and clarify whether it can be presented in the universal form.

The universal form of the quasihomogeneous solution can be easily seen in the situation of profiles also. In the AA there was no specific space scale because the consumption took place homogeneously from all space points of the system. Here in the situation of profiles there is the elementary space scale and one can choose the space scale as to have that the linear size of ER around the droplet is growing202020Certainly, the power has to be conserved. as $`t^{1/2}`$. The time scale has to be chosen as to get that in the free volume equal to the total volume of the system one can see the appearance of one droplet in the unit of time. As long as the functional dependencies of the nucleation rate and the radius of ER are not identical one can do such a renormalization without any problems. So, we see that the pseudohomogeneous case allows the universal description.

The process of the heterogeneous centers exhaustion destroys this universality and one has to act as in212121Here we use slightly more simple way. . The total number of droplets has to be approximately calculated as

$$N_{total}=\eta _{tot}[1\mathrm{exp}(\frac{N_{hom}}{\eta _{tot}})]$$
(13)
where $`N_{hom}`$ is the number of the droplets appeared in the quasihomogeneous situation (under the same parameters). This formula can be also used for all approximate models described earlier.

For the numerical simulation it was convenient to consider the cube box with a size $`10`$. The rate of the ER growth is chosen as

$$\frac{dR}{dt}=100t^{1/2}$$

where $`R`$ is the radius of ER. The rate of nucleation is chosen as to have one attempt of a new droplet formation in the system during $`dt=0.002`$. This attempt is governed by the random procedure. It may lead to the point in one of the ER and then no droplet will be formed. In the opposite situation when the point is indicated out of all ER of the already existing droplets there will be a new formation of a droplet.

One has to stress that the random procedure has one specific negative feature. In the standard numerical procedures the next random coordinate is calculated on the base of the previous ones. So, if the current coordinate lies near the center of the already existing ER then the next coordinate will be also near the center of another ER. These correlations lead to the necessity to consider the large system. In the system under consideration the number of droplets appeared in the quasihomogeneous situation will be near $`500`$. Nevertheless the square mean fluctuation will be about $`20`$. The careful consideration can show that the error induced by the substitution of the periodic boundary conditions by the zero ones has the same power as the mean square error. It can be directly seen by the numerical simulation. It is explained by the evident notation that the characteristic overlapping of profiles is about the mean profile size. We shall call this feature as the property of ”moderate overlapping”. This fact can be proven analytically. One can also analytically prove that the effect of fluctuations is really caused by the mentioned phenomena.

The mean value of the total droplets number is equal to $`504.8`$ (under the zero boundary conditions). This value has to be put into the previous formula.

The avalanche character of the vapor consumption is illustrated by fig. 2-4. Three different moments of time $`t=0.5`$, $`t=1`$ and $`t=1.5`$ are chosen as characteristic values. The cross section is drawn. The dashed regions correspond to the ER of the already existing droplets. The black regions correspond to the overlapping222222Only when the distance between centers is approximately the odd one. of ER.

The number of heterogeneous centers in such a system can be arbitrary. Certainly the effects of the centers exhaustion will be important when the number of centers is small (in comparison with $`N_{hom}=504.8`$). The pictures for $`\eta _{tot}=50`$ are drawn in fig. 5-7 for $`t=1.5`$, $`t=3`$, $`t=6`$. One can see that the number of ER is smaller than in the quasihomogeneous case. The size of ER when the free volume is going to be exhausted is larger than the size of ER in the quasihomogeneous case. The time necessary to cover all volume by ER is greater than in the quasihomogeneous case. It doesn’t mean that the duration of the nucleation period will be longer (simply all centers will be exhausted and this means the end of nucleation). Moreover, the duration of the nucleation period in the situation of the relatively small number of heterogeneous centers will be shorter than in the quasihomogeneous case.

One can also see that the avalanche character of the vapor consumption here will be more smooth than in the quasihomogeneous case. Certainly, in the quasihomogeneous case the appearance of the new ER helps to consume the vapor phase in the avalanche manner. But in the situation with the small number of centers there is no need to consider the process carefully because the exhaustion of centers leads to the evident result of condensation \- the number of the droplets equals to the number of centers.

Now it is evident that the main object of our interest will be the quasihomogeneous case. The relative rate of nucleation in this case is shown in fig. 8. Here the rate of nucleation is averaged over $`100dt0.2`$ and over $`16`$ attempts. So, the rate of nucleation is rather smooth function.

The relative rate of nucleation is compared in fig.8 with the mentioned models. Certainly, the rate of nucleation defines the spectrum of sizes when we take as the size of embryo those characteristic which has the rate of growth independent on the value of size. For the diffusion regime this characteristic is the number of molecules in the power $`2/3`$.

One can see in fig. 8 three different curves and some solitary points. The solitary points correspond to the numerical simulation of the quasihomogeneous case and three curves correspond to three models in the quasihomogeneous case.

The shortest spectrum is in the first model. The careful look shows that this line is doubled. This occurs because there the ideal variant of the first model is also drawn. This ideal variant corresponds to $`W_{free}/W_{total}1`$ in the subintegral function. The coincidence means that the main role in the first model is played by the relatively big droplets which were formed at $`W_{free}=W_{total}`$.

The longest spectrum corresponds to the second model. This curve is very close to the intermediate curve which corresponds to the third model. The approximate coincidence of the second and the third models shows that both of them are valid and the role of the relatively big droplets here is the main one.

One also see that the first model isn’t too far from the real solution. This allows to present the rigorous estimates for the nucleation rate. Certainly the first model is the estimate of the real process from below. It gives the number of the droplets about $`20`$ percents less than the numerical simulation.

An estimate for the nucleation rate from above can be gotten by the following way. From the first model it follows that until $`t=0.52`$ (practically this case is drawn in fig. 2) the rate of nucleation is near the ideal value and the deviation is less than $`15`$ percents. So, one can say that the period $`0<t<0.52`$ corresponds to the absence of overlapping (the first model is the estimate from above). Then one can consider the process where the total volume is exhausted only by the ER of the droplets appeared at $`0<t<0.52`$ in a random manner. The distribution of the centers of ER of such droplets is evidently random. This model certainly gives the estimate from above for the nucleation process. The total number of the droplets is only $`15`$ percents greater than the result of the numerical simulation. As a conclusion one can state that two suitable estimates from below and above are obtained.

The proximity of the last estimate to the real solution justifies the supposition that the main role in vapor consumption belongs to the droplets of the relatively big sizes appeared in the system practically free from the ER. This supposition can be also justified in the analytical manner.

One can see that the second and the third models are rather close to the real solution but don’t coincide with it. There are at least two reasons of such deviation. The first one is the presence of the strong correlations in the real system - if two ER overlap in some moment of time then the power of overlapping can only grow in time. It hasn’t a random character as it is stated in the second and third models.

This effect can be taken into account in a rather simple manner. It is sufficient to consider two spheres and calculate the power of overlapping as the function of the distance and time (it is the simple geometrical problem). Unfortunately the answer can be written only in a very complicate form. If we have two ER with radii $`R_1`$ and $`R_2`$ correspondingly at a distance $`l`$ between their centers and $`l>max(R_1,R_2)`$ then the volume of overlapping is

$$V_{over}=\frac{2\pi R_1^3}{3}(12cos\phi _1+cos^3\phi _1)+\frac{2\pi R_2^3}{3}(12cos\phi _2+cos^3\phi _2)$$

where

$$cos\phi _1=\frac{R_2^2+R_1^2+l^2}{2R_1l}$$

$$cos\phi _2=\frac{R_1^2+R_2^2+l^2}{2R_2l}$$

Certainly, this result can not lead to the compact form of the balance equation. It will be difficult to solve it analytically.

The second reason is the ”moderate overlapping” problem. This property means that actually there is an interaction through overlapping in ensemble of several droplets. Earlier this property was extracted  in a case of a special effective length of ER. Now we see that this property has a rather general sense. The way to solve this problem proposed in  is very complicate and leads to some uncertain relations.

How one can overcome all these problems? Actually one has no need to do it. The simple numerical simulation takes into account all these effects and gives the universal solution. Really we need only one number - the total number of appeared droplets. It is known. Then one can forget about all mentioned difficulties.

Now one can analyze the heterogeneous case explicitly. The suitable approximation is given by (13). One has to substitute instead of $`N_{hom}`$ the number of droplets given by the corresponding model.

The relative error of approximation (13) is drawn in fig. 9 for the first model, in fig. 10 for the second model, in fig. 11 for the third model. It is rather small for all models. For the third model it is practically negligible. It is clear because the third model is based on the free volume approximation. Then the source of error can be found only in exhaustion of centers without any influence on the growing of ER. Without this influence the power of exhaustion can not essentially act on the process of nucleation.

One can fulfill the same analysis for the numerical simulation. In fig. 12 the relative error of (13) for numerical simulation is drawn. Here in (13) the value $`N_{hom}=504.8`$ from the numerical simulation is used. The result is compared with the computer simulation of heterogeneous condensation. This simulation is rather simple. One can take the procedure for the quasihomogeneous case but put the center of the new droplet with probability $`\eta /\eta _{tot}`$. Every time when this point will be out of ER we shall reduce $`\eta `$ as $`\eta \eta 1`$.

One can see that the relative error is very small. We don’t use the averaging over (this is the reason why there is no smooth curve) many attempts in order to see that the error of (13) has the scale of the mean square error of numerical simulation232323For the system with $`500`$ droplets.. So, there is no need to use the more sophisticated approach.

The solution of the problem now is completed.

The generalization for the conditions of dynamic type is absolutely analogous to . The convergence due to avalanche consumption is more weak and one has to use instead of approximation (13) more sophisticated procedure described in . Certainly, the universal constants have to be calculated by the numerical simulation with profiles.

The generalization for the arbitrary regime of the droplets growth can be done absolutely analogous to . This generalization is based on the similarity of the functional forms obtained here and in the AA. This similarity lies in the base of universality formulated in , .

One can see that the theory of condensation with profiles taken into account presents the picture which is absolutely different from the AA. Nevertheless in many situations the result of experiment coincides with the result of the AA. One has to explain this coincidence. It is rather formal one.

Really, in any experiment it is more convenient to have a small system and to get many droplets. The rate of nucleation has to be taken as a rather high one. So, the supersaturation is relatively high and parameter $`\sigma ^1`$ isn’t a real small parameter of a theory242424 It isn’t necessary for consideration here, but it has to be small due to the possibility of thermodynamic description of the critical embryo.. Then as it is shown in  the AA gives the write qualitative result despite the wrong base of consideration. The reason lies in the fact that at small $`\sigma `$ the main quantity of a substance is lying in the tail of profile. The tail of profile is rather thin and can be be taken into account by the AA. In  the correction term for the AA at small $`\sigma `$ is also presented.

The last important feature to mention is the movement of the embryos boundaries. This problem is widely discussed in the determination of the rate of regular growth for the supercritical embryos. In different systems the effect of influence of the boundary movement on the rate of growth is different. We have to note that in theory presented here the rate of the embryos growth is an external value which is assumed to be known252525It is really known practically for all systems..

Another problem is the adequate account of the effect of boundary movement in construction of the ER. One can see that in the first part of publication it is already shown that the effect of the boundary movement is small. Here we shall present the abstract arguments for such conclusion.

To use the thermodynamic approach the initial power of the mother phase metastability has to be relatively small. Together with the Maxwell’s rule it leads to the following final result of the phase transition: ”Only relatively small part of the system volume is occupied by the new phase.” It isn’t in contradiction with the property that all volume is occupied by ER. So, the final state of the system is the practically saturated mother phase in practically all volume of the system and the small volume (distributed over all system) occupied by a new phase.

As the result one can see that the process of a substance consumption (extraction) leads to the saturation in a volume relatively large in comparison with a volume of the new phase embryo.

The mother phase can not be undersaturated (then there will be the disappearance of embryos). So, as long as even the saturated phase has to be spread on large distances $`l_0`$ one can state that the growth of embryo produces the perturbation over the large distances $`l>l_0`$. To have an interruption (relative interruption in comparison with an ideal nucleation rate) of a new phase formation one needs a very small reduction of the power of metastability262626Relative reduction has to be $`\mathrm{\Gamma }^1`$ where $`\mathrm{\Gamma }1`$ has the scale of the number of molecules in the critical embryo.. So, this reduction is attained at the distances $`l^{}>l`$ which are very large in comparison with the embryos linear size. Then one can use the point source approximation as it was done in the first part and forget about the boundaries movement. The negligible character of the boundary movement is proven now for all possible systems.

The heat extraction and account of all other intensive parameters of description can be done analogously to .

Fig. 1

The form of $`f(\beta )`$.

Fig. 2

The cross section of the system at $`t=0.5`$ for the quasihomogeneous situation.

Fig. 3

The cross section of the system at $`t=1`$ for the quasihomogeneous situation.

Fig. 4

The cross section of the system at $`t=1.5`$ for the quasihomogeneous system.

Fig. 5

The cross section of the system at $`t=1.5`$ for $`\eta _{tot}=50`$.

Fig. 6

The cross section of the system at $`t=3`$ for $`\eta _{tot}=50`$.

Fig. 7

The cross section of the system at $`t=6`$ for $`\eta _{tot}=50`$.

Fig. 8

Comparison of different models in the quasihomogeneous situation.

Fig. 9

Relative error of the quasihomogeneous approach in the first model.

Fig. 10

Relative error of the quasihomogeneous approach in the second model.

Fig. 11

Relative error of the quasihomogeneous approach in the third model.

Fig. 12

Relative error of the quasihomogeneous approach in the universal simulation.


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# Untitled Document

On non-$`L^2`$ solutions to the Seiberg–Witten equations

by

Christoph Adam, Bruno Muratori and Charles Nash

Institut für Theoretische Physik Department of Mathematical Physics,

Universität Karlsruhe, National University of Ireland,

Germany. Maynooth,

Ireland.

Abstract: We show that a previous paper of Freund describing a solution to the Seiberg–Witten equations has a sign error rendering it a solution to a related but different set of equations. The non-$`L^2`$ nature of Freund’s solution is discussed and clarified and we also construct a whole class of solutions to the Seiberg–Witten equations.

$`\mathrm{\S }`$ 1. Introduction

With the introduction of the Seiberg–Witten equations  there come a wealth of results on four manifold theory and a new improved point of view on Donaldson theory with an Abelian gauge theory supplanting a non-Abelian one—cf.  for a review.

An important vanishing theorem of , reminiscent of the Lichernowicz–Weitzenböck vanishing theorems, shows that there are no non-trivial solutions to the Seiberg–Witten equations on four manifolds with non-negative Riemannian scalar curvature. However one can have non-trivial solutions which are singular in some way—for example one could have a non-trivial solution which was not $`L^2`$: in  Freund describes such a non-$`L^2`$ to the Seiberg–Witten equations on $`𝐑^4`$. Unfortunately a sign discrepancy in  means that the expressions given there obey equations which differ from the Seiberg–Witten equations in a certain sign. These other equations also admit $`L^2`$ solutions as well as non-$`L^2`$ ones and so Freund’s equations are fundamentally different from the Seiberg–Witten equations.

In $`\mathrm{\S }\mathrm{\hspace{0.17em}2}`$ we describe the Seiberg–Witten equations in a fairly explicit manner so as to expose notational conventions and matters of signs. In section $`\mathrm{\S }\mathrm{\hspace{0.17em}3}`$ we give the details concerning Freund’s work and then in section $`\mathrm{\S }\mathrm{\hspace{0.17em}4}`$ we give an $`L^2`$ solution of Freund’s equations and a class of solutions to the Seiberg–Witten equations.

$`\mathrm{\S }`$ 2. The Seiberg–Witten equations

If $`M`$ is an oriented Riemannian four manifold with metric $`g_{ij}`$ then the data we need for the Seiberg–Witten equations are a $`U(1)`$ connection $`A_i`$ on $`M`$ and a local spinor field $`M`$.

If $`F_{ij}`$ is the curvature of $`A_i`$, so that its self-dual part $`F_{ij}^+`$ is given by $`F_{ij}^+=1/2(F_{ij}+(\sqrt{g}/2)ϵ_{ijkl}F^{kl})`$, then the Seiberg–Witten equations are

$$\begin{array}{cc}\hfill F_{ij}^+& =\frac{i}{2}\overline{M}\mathrm{\Gamma }_{ij}M\hfill \\ \hfill \mathrm{\Gamma }^iD_iM& =0\hfill \end{array}$$
$`(2.1)`$
where $`\mathrm{\Gamma }_i`$ are the gamma matrices**Our conventions for the $`\mathrm{\Gamma }_i`$ are: $`\mathrm{\Gamma }_0=\left(\begin{array}{cc}0& I\\ I& 0\end{array}\right)`$, $`\mathrm{\Gamma }_i=\left(\begin{array}{cc}0& i\sigma ^i\\ i\sigma ^i& 0\end{array}\right)`$, and $`\mathrm{\Gamma }_5=\mathrm{\Gamma }_0\mathrm{\Gamma }_1\mathrm{\Gamma }_2\mathrm{\Gamma }_3`$ where $`\sigma ^i`$ are the Pauli matrices. satisfying $`\{\mathrm{\Gamma }_i,\mathrm{\Gamma }_j\}=2g_{ij}I`$, and $`D_i`$ and $`\mathrm{\Gamma }_{ij}`$ are given by

$$D_i=_i+iA_i,\mathrm{\Gamma }_{ij}=\frac{1}{2}[\mathrm{\Gamma }_i,\mathrm{\Gamma }_j]$$
$`(2.2)`$
In  Witten also quotes the equations using the two component spinor formalism of L. Witten and Penrose, cf. , where the Gamma matrices make no explicit appearance. In this spinor form the equations are

$$\begin{array}{cc}\hfill _{A^{}B^{}}& =\frac{i}{2}\left(_A^{}\stackrel{~}{}_B^{}+_B^{}\stackrel{~}{}_A^{}\right)\hfill \\ \hfill 𝒟_{AA^{}}^A^{}& =0\hfill \end{array}$$
$`(2.3)`$
We now give a short summary of the relevant properties of the spinor formalism that we need here.

With a Riemannian metric of signature $`(+,+,+,+)`$ the 4 components of a $`4`$-vector $`v_a(v_0,v_1,v_2,v_3)`$ are represented by a $`2\times 2`$ matrix which is denoted by $`v_{AA^{}}`$ and given by

$$v_{AA^{}}=\frac{1}{\sqrt{2}}\left(\begin{array}{cc}v_0+iv_3& iv_1+v_2\\ iv_1v_2& v_0iv_3\end{array}\right)$$
$`(2.4)`$
This expression for $`v_{AA^{}}`$ can be written as a linear combination of what are known as the Infeld–van der Waerden matrices $`g_{AA^{}}^a`$ defined by

$$g_{AA^{}}^0=\frac{1}{\sqrt{2}}\left(\begin{array}{cc}1& 0\\ 0& 1\end{array}\right),g_{AA^{}}^i=\frac{i}{\sqrt{2}}\sigma ^i,i=1,2,3$$
$`(2.5)`$
where $`\sigma ^i`$ are the usual Pauli matrices so that

$$\sigma ^1=\left(\begin{array}{cc}0& 1\\ 1& 0\end{array}\right),\sigma ^2=\left(\begin{array}{cc}0& i\\ i& 0\end{array}\right),\sigma ^3=\left(\begin{array}{cc}1& 0\\ 0& 1\end{array}\right)$$
$`(2.6)`$
Using the $`g_{AA^{}}^a`$’s the linear combination mentioned above is given by

$$v_{AA^{}}=v_ag_{AA^{}}^a$$
$`(2.7)`$
and more generally if we have a tensor $`T_{a_1a_2\mathrm{}a_n}`$ it becomes $`𝒯_{A_1A_1^{}A_2A_2^{}\mathrm{}A_nA_n^{}}`$ where

$$𝒯_{A_1A_1^{}A_2A_2^{}\mathrm{}A_nA_n^{}}=T_{a_1a_2\mathrm{}a_n}g_{A_1A_1^{}}^{a_1}g_{A_2A_2^{}}^{a_2}\mathrm{}g_{A_nA_n^{}}^{a_n}$$
$`(2.8)`$
In this formalism spinor indices are raised and lowered with the matrix $`ϵ_{AB}`$ defined by

$$ϵ_{AB}=\left(\begin{array}{cc}0& 1\\ 1& 0\end{array}\right)=ϵ^{AB}$$
$`(2.9)`$
For example, for one spinor index, one can write

$$v^A=ϵ^{AB}v_B,v_B=v^Aϵ_{AB}$$
$`(2.10)`$
An involution can also be defined on a spinor $`v^A`$ taking it to a spinor $`\stackrel{~}{v}^A`$ defined by

$$v^A=\left(\begin{array}{c}\alpha \\ \beta \end{array}\right),\stackrel{~}{v}^A=\left(\begin{array}{c}\overline{\beta }\\ \overline{\alpha }\end{array}\right)$$
$`(2.11)`$
where bar means complex conjugate.

Simplification occurs if the tensor is antisymmetric such as the curvature tensor $`F_{ij}`$: in that case one can verify that its spinor version $`_{AA^{}BB^{}}`$ is a linear combination of $`ϵ_{A^{}B^{}}`$ and $`ϵ_{AB}`$. More precisely one finds that

$$F_{ij}g_{AA^{}}^ig_{BB^{}}^j=_{AA^{}BB^{}}=_{AB}ϵ_{A^{}B^{}}+_{A^{}B^{}}ϵ_{AB}$$
$`(2.12)`$
Moreover it also turns out that $`_{A^{}B^{}}`$ and $`_{AB}`$ are the spinor projections of the self-dual and anti-self-dual parts of $`F_{ij}`$ respectively; i.e. one can check that

$$F_{ij}^+g_{AA^{}}^ig_{BB^{}}^j=_{A^{}B^{}}ϵ_{AB},F_{ij}^{}g_{AA^{}}^ig_{BB^{}}^j=_{AB}ϵ_{A^{}B^{}}$$
$`(2.13)`$
Now we return to the Seiberg–Witten equations and carry out the translation from the conventional to the spinor form. Starting with the Dirac equation we write

$$M=\left(\begin{array}{c}\alpha \\ \beta \\ 0\\ 0\end{array}\right)\left(\begin{array}{c}^A^{}\\ 0\\ 0\end{array}\right)$$
$`(2.14)`$
and then the Dirac equation

$$\mathrm{\Gamma }^iD_iM=0$$
$`(2.15)`$
becomes

$$\sqrt{2}g_{AA^{}}^iD_i^A^{}=0$$
$`(2.16)`$
which we rewrite as

$$𝒟_{AA^{}}^A^{}=0,\text{ with }𝒟_{AA^{}}=\frac{1}{\sqrt{2}}\left(\begin{array}{cc}D_0+iD_3& iD_1+D_2\\ iD_1D_2& D_0iD_3\end{array}\right)$$
$`(2.17)`$
which is the desired form. Moving on to the other equation

$$F_{ij}^+=\frac{i}{2}\overline{M}\mathrm{\Gamma }_{ij}M$$
$`(2.18)`$
we first display this equation in full as

$$\begin{array}{cc}& \frac{1}{2}\left(\begin{array}{cccc}0& F_{01}+F_{23}& F_{02}F_{13}& F_{03}+F_{12}\\ F_{01}F_{23}& 0& F_{03}+F_{12}& F_{13}F_{02}\\ F_{13}F_{02}& F_{12}F_{03}& 0& F_{01}+F_{23}\\ F_{12}F_{03}& F_{02}F_{13}& F_{01}F_{23}& 0\end{array}\right)=\hfill \\ & \\ & \frac{1}{2}\left(\begin{array}{cccc}0& \overline{\beta }\alpha +\overline{\alpha }\beta & i\overline{\beta }\alpha i\overline{\alpha }\beta & |\alpha |^2|\beta |^2\\ \overline{\beta }\alpha \overline{\alpha }\beta & 0& |\alpha |^2|\beta |^2& i\overline{\beta }\alpha +i\overline{\alpha }\beta \\ i\overline{\beta }\alpha +i\overline{\alpha }\beta & |\alpha |^2+|\beta |^2& 0& \overline{\beta }\alpha +\overline{\alpha }\beta \\ |\alpha |^2+|\beta |^2& i\overline{\beta }\alpha i\overline{\alpha }\beta & \overline{\beta }\alpha \overline{\alpha }\beta & 0\end{array}\right)\hfill \end{array}$$
$`(2.19)`$
and then find that

$$F_{ij}^+g_{AA^{}}^ig_{BB^{}}^j=\frac{i}{2}\overline{M}\mathrm{\Gamma }_{ij}Mg_{AA^{}}^ig_{BB^{}}^j$$
$`(2.20)`$
becomes

$$_{A^{}B^{}}ϵ_{AB}=𝒯_{A^{}B^{}}ϵ_{AB}$$
$`(2.21)`$
i.e.

$$_{A^{}B^{}}=𝒯_{A^{}B^{}}$$
$`(2.22)`$
where

$$_{A^{}B^{}}=\frac{1}{2}\left(\begin{array}{cc}iF_{01}+iF_{23}+F_{13}F_{02}& iF_{12}iF_{03}\\ iF_{12}iF_{03}& iF_{01}iF_{23}+F_{13}F_{02}\end{array}\right)$$
$`(2.23)`$
and

$$𝒯_{A^{}B^{}}=\frac{1}{2}\left(\begin{array}{cc}2i\overline{\alpha }\beta & i|\alpha |^2+i|\beta |^2\\ i|\alpha |^2+i|\beta |^2& 2i\alpha \overline{\beta }\end{array}\right)$$
$`(2.24)`$
On can now readily inspect equations 2.19 and 2.22, 2.23, 2.24 and confirm that the conventional and the spinor form of the equations agree.

Also we can compute the matrix of components $`(i/2)(_A^{}\stackrel{~}{}_B^{}+_B^{}\stackrel{~}{}_A^{})`$ and verify that it is equal to $`𝒯_{A^{}B^{}}`$. Doing this we find that, if we start with $`^A^{}=(\alpha ,\beta )`$ and use 2.10 and 2.11, we obtain

$$\begin{array}{cc}\hfill \frac{i}{2}((_A^{}\stackrel{~}{}_B^{}+_B^{}\stackrel{~}{}_A^{})& =\frac{1}{2}\left(\begin{array}{cc}2i\overline{\alpha }\beta & i|\alpha |^2+i|\beta |^2\\ i|\alpha |^2+i|\beta |^2& 2i\alpha \overline{\beta }\end{array}\right)\hfill \\ & =𝒯_{A^{}B^{}},\hfill \end{array}$$
$`(2.25)`$
as it should. We now turn to the explicit Fermion and gauge field considered by Freund.

$`\mathrm{\S }`$ 3. Freund’s equations

In  Freund chooses

$$\begin{array}{cc}\hfill A_i=\frac{1}{2r(rz)}\left(\begin{array}{c}0\\ y\\ x\\ 0\end{array}\right),\text{ and }^A^{}& =\frac{1}{2r\sqrt{r(rz)}}\left(\begin{array}{c}xiy\\ rz\end{array}\right)\hfill \\ \hfill \stackrel{~}{}^A^{}& =\frac{1}{2r\sqrt{r(rz)}}\left(\begin{array}{c}(rz)\\ x+iy\end{array}\right)\hfill \end{array}$$
$`(3.1)`$
for which one readily verifies that

$$𝒟_{AA^{}}^A^{}=0$$
$`(3.2)`$
so that $`^A^{}`$ is indeed a zero mode.

To check the other equation we compute the curvature and find that, if $`F_{ij}=_iA_j_jA_i`$, one has

$$\begin{array}{cc}\hfill F_{0i}& =0,F_{12}=\frac{z}{2r^3},F_{13}=\frac{y}{2r^3},F_{23}=\frac{x}{2r^3}\hfill \\ \hfill _{A{}_{}{}^{}B_{}^{}}& =\frac{1}{4r^3}\left(\begin{array}{cc}yix& iz\\ iz& y+ix\end{array}\right)\hfill \end{array}$$
$`(3.3)`$
On the other hand one also finds that

$$\begin{array}{cc}\hfill \frac{i}{2}(_A^{}\stackrel{~}{}_B^{}+_B^{}\stackrel{~}{}_A^{})& =\frac{1}{4r^3}\left(\begin{array}{cc}y+ix& iz\\ iz& yix\end{array}\right)\hfill \\ & =_{A{}_{}{}^{}B_{}^{}}\hfill \end{array}$$

so that $`_{A{}_{}{}^{}B_{}^{}}(i/2)(_A^{}\stackrel{~}{}_B^{}+_B^{}\stackrel{~}{}_A^{})`$ and Freund’s equations are

$$\begin{array}{cc}\hfill _{A^{}B^{}}& =\frac{i}{2}\left(_A^{}\stackrel{~}{}_B^{}+_B^{}\stackrel{~}{}_A^{}\right)\hfill \\ \hfill 𝒟_{AA^{}}^A^{}& =0\hfill \end{array}$$
$`(3.4)`$
The Seiberg–Witten’s equations are known to admit no non-trivial regular $`L^2`$ solutions in flat space (or spaces of positive scalar curvature) so Freund was concerned to point out that his fields provide an example of a non-trivial solution which is not $`L^2`$. Unfortunately, as we have seen, Freund’s fields, though not $`L^2`$, are not solutions to the Seiberg–Witten equations.

Since Freund’s fields are static and have a connection with $`A_0=0`$ it is natural to consider them in $`𝐑^3`$. We now do this letting $`𝐀=(A_1,A_2,A_3)`$ be the connection in $`𝐑^3`$ and denote its curvature components by $`\widehat{F}_{ab}`$, $`a,b=\mathrm{1..3}`$. We obtain thereby the three dimensional Freund equations

$$\begin{array}{cc}\hfill \widehat{F}_{ab}& =ϵ_{abc}\overline{M}\sigma ^cM,a,b=\mathrm{1..3}\hfill \\ \hfill \text{/}_AM& =0,\text{where }\text{/}_A=i\sigma ^a(_a+iA_a)\hfill \end{array}$$
$`(3.5)`$
In similar fashion we could also have obtained the three dimensional Seiberg–Witten equations—cf. —and, as in four dimensions, these differ from Freund’s only in the sign of the quadratic Fermion term. They are

$$\begin{array}{cc}\hfill \widehat{F}_{ab}& =ϵ_{abc}\overline{M}\sigma ^cM,a,b=\mathrm{1..3}\hfill \\ \hfill \text{/}_AM& =0,\text{where }\text{/}_A=i\sigma ^a(_a+iA_a)\hfill \end{array}$$
$`(3.6)`$
There is also a vanishing theorem which does not allow non trivial solutions in flat space so that there are no regular $`L^2`$ solutions to the equations 3.6 in $`𝐑^3`$. However there is no such restriction on the Freund’s equations 3.5. In the next section we show how to construct examples of singular non-$`L^2`$ solutions to the Seiberg–Witten equations and regular solutions to of Freund’s equations which are $`L^2`$ in $`𝐑^3`$.

$`\mathrm{\S }`$ 4. The Freund and Seiberg–Witten equations in three dimensions

First of all we simply note that Freund’s equations 3.5 (or indeed 3.4) admit the following regular solution which is $`L^2`$ in $`𝐑^3`$.

$$\begin{array}{cc}\hfill ^A^{}& =\frac{\sqrt{12}(\mathrm{𝟏}+i\stackrel{}{\sigma }\stackrel{}{r})}{(1+r^2)^{3/2}}\left(\begin{array}{c}1\\ 0\end{array}\right)\hfill \\ \hfill A_i& =\frac{3}{(1+r^2)^2}\left(\begin{array}{c}2xz2y\\ 2yz+2x\\ 1r^2+2z^2\end{array}\right)\hfill \end{array}$$
$`(4.1)`$
as may be checked easily.

Finally we would like to display some (necessarily singular) solutions to the three dimensional Seiberg–Witten equations 3.6; they will also of course be solutions of the full Seiberg–Witten equations 2.1 or 2.3. In fact we construct a whole class of such solutions parametrised by an arbitrary holomorphic function.

First we need some facts about the Dirac equation in 3.6. A spinor $`M`$ that obeys the Dirac equation $`\text{/}_AM=0`$ of 3.6 must obey the condition

$$_a\mathrm{\Sigma }^a=0,\text{where }\mathrm{\Sigma }^a=\overline{M}\sigma ^aM$$
$`(4.2)`$
The connection $`A_i`$ in the Dirac equation can be expressed in terms of the zero mode $`M`$ by writing

$$\begin{array}{cc}\hfill A_i& =\frac{1}{\sqrt{\mathrm{\Sigma }^a\mathrm{\Sigma }^a}}\left(\frac{1}{2}ϵ_{ijk}_j\mathrm{\Sigma }_k+Im\overline{M}_iM\right)\hfill \\ & =\frac{1}{2}ϵ_{ijk}\left(_j\mathrm{ln}\sqrt{\mathrm{\Sigma }^a\mathrm{\Sigma }^a}\right)N_k\frac{1}{2}ϵ_{ijk}_jN_kIm\overline{\widehat{M}}_i\widehat{M}\hfill \\ \hfill \text{where }N^a& =\frac{\mathrm{\Sigma }^a}{\sqrt{\mathrm{\Sigma }^b\mathrm{\Sigma }^b}},\text{and }\widehat{M}=\frac{M}{\sqrt{\overline{M}M}}\hfill \end{array}$$
$`(4.3)`$
Now, if $`\chi `$ is the complex variable

$$\chi =\frac{x+iy}{r^2}$$
$`(4.4)`$
and $`GG(\chi ,\overline{\chi })`$ is a function of $`\chi `$ and $`\overline{\chi }`$, we obtain a new class of zero modes $`M^G`$ where

$$\begin{array}{cc}\hfill M^G& =e^{G/2}M^0\hfill \\ \hfill \text{and }M^0& =\frac{1}{r^3}\left(\begin{array}{c}z\\ x+iy\end{array}\right)\hfill \end{array}$$
$`(4.5)`$
The corresponding connection $`A_i^G`$ is found using formula 4.3 and is given by

$$A_i^G=\frac{1}{2}ϵ_{ijk}_jGN_k$$
$`(4.6)`$
We note that the spinor $`M^0`$ is singular and non-$`L^2`$. For doing calculations it is also useful to note that $`M^0`$ is a solution of the free Dirac equation

$$\text{/}M^0=0$$
$`(4.7)`$
and that the spin density for $`M^G`$ satisfies

$$\begin{array}{cc}\hfill \overline{M^G}\sigma ^aM^G& =e^G\overline{M^0}\sigma ^aM^0\hfill \\ \hfill \text{where }\overline{M^0}\sigma ^aM^0& =\frac{N^a}{r^4}=\frac{1}{2i}(\overline{\chi })\times (\chi )\hfill \end{array}$$
$`(4.8)`$
The corresponding curvature $`\widehat{F}_{ij}^G`$ is

$$\begin{array}{cc}\hfill \widehat{F}_{ij}^G& =\frac{ϵ_{ijk}}{2}[G_{,\chi }(\chi _{,kl}N_l+\chi _{,k}N_{l,l}\chi _{,ll}N_k\chi _{,l}N_{k,l})+\hfill \\ & G_{,\overline{\chi }}(\overline{\chi }_{,kl}N_l+\overline{\chi }_{,k}N_{l,l}\overline{\chi }_{,ll}N_k\overline{\chi }_{,l}N_{k,l})\hfill \\ & (G_{,\chi \chi }\chi _{,l}\chi _{,l}+G_{,\overline{\chi }\overline{\chi }}\overline{\chi }_{,l}\overline{\chi }_{,l}+2G_{,\chi \overline{\chi }}\chi _{,l}\overline{\chi }_{,l})N_k]\hfill \end{array}$$
$`(4.9)`$
After some tedious algebra we find that only the coefficient of $`G_{,\chi \overline{\chi }}`$ is non-zero and that

$$\chi _{,k}\overline{\chi }_{,k}=\frac{2}{r^4}$$
$`(4.10)`$
and hence

$$\widehat{F}_{ij}^G=\frac{2ϵ_{ijk}}{r^4}G_{,\chi \overline{\chi }}N_k$$
$`(4.11)`$
But to have a solution of the Seiberg–Witten equations we must require that

$$\widehat{F}_{ij}^G=ϵ_{ijk}\overline{M^G}\sigma ^kM^G$$
$`(4.12)`$
and this means that

$$\begin{array}{cc}\hfill \frac{2}{r^4}G_{,\chi \overline{\chi }}N_k& =\overline{M^G}\sigma ^kM^G\hfill \\ \hfill G_{,\chi \overline{\chi }}& =\frac{1}{2}e^G\hfill \end{array}$$
$`(4.13)`$
as may be easily checked. But this equation for $`G`$ is nothing other than the Liouville equation in the “target space coordinate” $`\chi `$ with the “wrong” sign; that is to say that the sign leads to the general singular solution

$$G=\frac{|f^{}(\chi )|^2}{(1f\overline{f})^2}$$
$`(4.14)`$
where $`f`$ is an arbitrary holomorphic function of $`\chi `$.

Hence any pair $`(M^G,A_i^G)`$ with $`G`$ given by 4.14 is a solution the Seiberg–Witten equations 3.6. In fact, these solutions resemble the two-dimensional solutions of the Seiberg–Witten equations that were discussed in . Their solutions emerged as solutions to the same Liouville equation 4.14, however the coordinate space variable $`x_+=x+iy`$ appears rather than the target space variable $`\chi `$ used here.

Finally we want to briefly describe the geometry of the spin density term $`\overline{M}\sigma ^aM`$. It is clearly rotationally symmetric around the $`z`$ axis and the integral curves of $`\overline{M^0}\sigma ^aM^0`$ are circles that touch the $`z`$ axis at the point $`z=0`$. If we restrict to the $`xz`$ plane, then these integral curves are the field lines of a dipole in two dimensions, and the vector field $`\overline{M^0}\sigma ^aM^0`$ restricted to that plane is a scalar function times the field of a dipole in two dimensions.

Acknowledgment:  BM gratefully acknowledges financial support from the Training and Mobility of Researchers scheme (TMR no. ERBFMBICT983476).

References

1.Witten E., Monopoles and four-manifolds, Math. Res. Lett., 1, 769–796, (1994).

2.Donaldson S. K., The Seiberg–Witten equations and 4-manifold topology, Bull. Amer. Math. Soc., 33, 45–70, (1996).

3.Freund P. G. O., Dirac monopoles and the Seiberg–Witten monopole equations, J. Math. Phys., 36, 2673–2674, (1995).

4.Penrose R. and Rindler W., Spinors and Space-time vol. 1, Cambridge University Press, (1984).

5.Loss M. and Yau H., Stability of Coulomb systems with magnetic fields III. Zero energy bound states of the Pauli operator, Commun. Math. Phys., 104, 283–290, (1986).

6.Nergiz S. and Sacioglu J., Liouville vortex and $`\varphi ^4`$ kink solutions of the Seiberg–Witten equations, J. Math. Phys., 37, 3753–3759, (1996).


text:
# INDIRECT CONSTRAINTS ON R-PARITY VIOLATING STOP COUPLINGS

## Acknowledgements

The author thanks the organizers of the XXXV Rencontres de Moriond for the pleasant atmosphere in which this work was presented. Many thanks also go to Fabio Zwirner for helpful discussions and to Guido Martinelli for useful communications.

## Appendix

We have calculated the contributions to $`K^0`$$`\overline{K}^0`$ mixing coming from the diagrams with $`R_p`$-violating (s)top couplings $`\lambda _{3jk}^{\prime \prime }`$. The calculation has been performed in the basis where the quark masses are diagonal, and all the flavor changing squark mass insertions have been neglected. We have also checked that in the minimal supergravity scenario considered in ref. $`^\mathrm{?}`$ the contributions coming from MSSM diagrams with quarks and charged higgs or squarks and charginos are negligible. The coefficients $`C_i`$ that appear in eq. (2) are:

$`C_1`$ $`=`$ $`{\displaystyle \underset{i,j=1}{\overset{3}{}}}{\displaystyle \frac{g^4}{128\pi ^2}}K_{i1}^{}K_{i2}K_{j1}^{}K_{j2}m_{u_i}^2m_{u_j}^2[I_0+2I_2/m_W^2+I_4/4m_W^4](m_{u_i}^2,m_{u_j}^2,m_W^2,m_W^2)`$
$`\stackrel{~}{C}_1`$ $`=`$ $`{\displaystyle \underset{i,j=1}{\overset{2}{}}}{\displaystyle \frac{1}{4\pi ^2}}|\lambda _{313}^{\prime \prime }\lambda _{323}^{\prime \prime }|^2[(O_{i2}^tO_{j2}^t)^2I_4(m_b^2,m_b^2,m_{\stackrel{~}{t}_i}^2,m_{\stackrel{~}{t}_j}^2)+(O_{i2}^bO_{j2}^b)^2I_4(m_{\stackrel{~}{b}_i}^2,m_{\stackrel{~}{b}_j}^2,m_t^2,m_t^2)]`$
$`C_5`$ $`=`$ $`{\displaystyle \underset{i=1}{\overset{2}{}}}{\displaystyle \frac{g^2}{4\pi ^2}}\lambda _{313}^{\prime \prime }\lambda _{323}^{\prime \prime }(O_{i2}^b)^2K_{31}^{}K_{32}m_t^2[I_2(m_{\stackrel{~}{b}_i}^2,m_W^2,m_t^2,m_t^2)+`$ (5)
$`{\displaystyle \frac{1}{4m_W^2}}I_4(m_{\stackrel{~}{b}_i}^2,m_W^2,m_t^2,m_t^2)+{\displaystyle \frac{1}{4m_W^2\mathrm{tan}^2\beta }}I_4(m_{\stackrel{~}{b}_i}^2,m_{H^+}^2,m_t^2,m_t^2)]`$
$`+`$ $`{\displaystyle \underset{i,j,k=1}{\overset{2}{}}}{\displaystyle \frac{g^2}{8\pi ^2}}\lambda _{313}^{\prime \prime }\lambda _{323}^{\prime \prime }O_{j2}^tO_{k2}^tK_{31}^{}K_{32}[V_{i1}^{}O_{j1}^t{\displaystyle \frac{m_t}{\sqrt{2}m_W\mathrm{sin}\beta }}V_{i2}^{}O_{j2}^t]\times `$
$`\left[V_{i1}O_{k1}^t{\displaystyle \frac{m_t}{\sqrt{2}m_W\mathrm{sin}\beta }}V_{i2}O_{k2}^t\right]I_4(m_b^2,m_{\stackrel{~}{\chi }_i^+}^2,m_{\stackrel{~}{t}_j}^2,m_{\stackrel{~}{t}_k}^2)`$
and $`C_4=C_5`$. In the above equations, $`K_{ij}`$ are the CKM matrix elements, $`O_{ij}^t`$ and $`O_{ij}^b`$ are the left-right mixing matrices of the stop and sbottom sectors, and $`V_{ij}`$ is the mixing matrix of positive charginos as defined in ref. $`^\mathrm{?}`$. The masses of the supersymmetric particles and the mixing angles at the electroweak scale have been calculated with ISAJET $`^\mathrm{?}`$, and the common scale $`M_S`$ has been chosen as the geometrical mean of squark and chargino masses. The functions $`I_n`$ result from integration over the Euclidean momentum $`\overline{k}`$ of the four particles circulating in the loop:

$$I_n(m_1^2,m_2^2,m_3^2,m_4^2)=_0^{\mathrm{}}\frac{\overline{k}^nd\overline{k}^2}{(\overline{k}^2+m_1^2)(\overline{k}^2+m_2^2)(\overline{k}^2+m_3^2)(\overline{k}^2+m_4^2)}$$
(6)
## References


text:
# 1 Flatness Problem

## 1 Flatness Problem

Albrecht and Magueijo proposed that a time varying speed of light c should not introduce changes in the curvature terms in the Einstein’s equations in the cosmological frame and that Einstein’s equations must still hold. Assuming that matter behaves as a perfect fluid, the equations of state can be written as,

$`P=(\gamma 1)\rho c^2(t).`$ (1)
Friedmann equations for a homogeneous space time, with c and G, as functions of time are,

$`{\displaystyle \frac{\dot{a}^2}{a^2}}={\displaystyle \frac{8\pi }{3}}G(t)\rho {\displaystyle \frac{Kc^2(t)}{a^2}}`$ (2)
$`\ddot{a}={\displaystyle \frac{4}{3}}\pi G(t)(\rho +{\displaystyle \frac{3p}{c^2(t)}})a`$ (3)
where $`\rho `$ and p are density and pressure of the matter, and K is the metric curvature parameter. Combining Eq.(2) and Eq.(3), the generalized conservation equation is,

$`\dot{\rho }+3{\displaystyle \frac{\dot{a}}{a}}(\rho +{\displaystyle \frac{p}{c^2}})=\rho {\displaystyle \frac{\dot{G}}{G}}+{\displaystyle \frac{3Kc\dot{c}}{4\pi Ga^2}}`$ (4)
We assume the conservation of ordinary matter; ie., the left hand side of Eq.(4) is zero. Thus the variations in c and G are such that the right hand side of Eq.(4) is identically zero. Assuming $`\rho a^{3\gamma }`$ and $`c(t)=c_0a^n`$,where $`c_0`$ and n are constants. The solution of the right hand side of Eq.(4), for $`3\gamma +2n20`$ is

$$G=\frac{3K(c_0)^2n}{4\pi \rho _0}\frac{a^{3\gamma +2n2}}{3\gamma +2n2}+B$$
(5)
and for, $`3\gamma +2n=2`$ is

$$G=\frac{3K(c_0)^2n}{4\pi \rho _0}\mathrm{ln}a+B$$
(6)
where B is a constant of integration. Thus the Friedmann equation for the $`3\gamma +2n2`$ case becomes

$`{\displaystyle \frac{\dot{a}^2}{a^2}}=B^{}a^{3\gamma }+{\displaystyle \frac{K(c_0)^2a^{2n2}(23\gamma )}{(3\gamma +2n2)}}`$ (7)
where B’is a constant. The curvature term in Eq.(2) vanishes as the scale factor evolves, if $`\ddot{a}>0`$ ie., $`\rho +\frac{3p}{c^2}<0`$ . Also the Eq.(4) gives the solution,

$`\rho a^{3\gamma }`$ for $`\ddot{G}=\ddot{c}=0`$ if $`\rho +\frac{p}{c^2}0`$

Using the equation of state, Eq.(1), these conditions imply

$`0\gamma <\frac{2}{3}`$

The scale factor evolves as

$`a(t)t^{\frac{2}{3}\gamma }`$ if $`\gamma >0`$

and

$`a(t)\mathrm{exp}(H_0(t)`$ if $`\gamma =0`$

For $`\gamma <\frac{2}{3}`$, the requirement $`\rho +\frac{3p}{c^2}<0`$ implies $`p<\frac{1}{3}\rho c^2`$, ie., the curvature term will vanish at large a only if the matter stress is gravitationally repulsive. From Eq.(7) it can be seen that the flatness problem can be solved for,

$`n{\displaystyle \frac{1}{2}}(23\gamma ).`$ (8)
This is exactly the same inequality, which Barrow derived without assuming energy conservation of ordinary matter$`^{\text{[4]}}`$.

## 2 Lambda Problem

To incorporate the cosmological constant term into the Friedmann equation, a vacuum stress is considered obeying the equation of state,

$`p_\mathrm{\Lambda }=\rho _\mathrm{\Lambda }c^2,`$ (9)
with

$`\rho _\mathrm{\Lambda }={\displaystyle \frac{\mathrm{\Lambda }c^2}{8\pi G}}0.`$ (10)
The Friedmann equation containing $`\rho _\mathrm{\Lambda }`$is,

$`{\displaystyle \frac{\dot{a}^2}{a^2}}={\displaystyle \frac{8}{3}}\pi G(\rho +\rho _\mathrm{\Lambda }){\displaystyle \frac{Kc^2}{a^2}}.`$ (11)
As the universe expands the term containing $`\rho _\mathrm{\Lambda }`$ should dominate. But observationally it is very small. This is the $`\mathrm{\Lambda }`$ problem. The conservation Eq.(4) generalised to include $`\rho _\mathrm{\Lambda }`$ is,

$`\dot{\rho }+3{\displaystyle \frac{\dot{a}}{a}}[\rho +{\displaystyle \frac{p}{c^2}}]=\dot{\rho _\mathrm{\Lambda }}(\rho +\rho _\mathrm{\Lambda }){\displaystyle \frac{\dot{G}}{G}}+{\displaystyle \frac{3Kc\dot{c}}{4\pi Ga^2}}.`$ (12)
We assume a form for the variation of G and $`\mathrm{\Lambda }`$ in terms of the scale factor as, $`G=G_0a^q`$ and $`\mathrm{\Lambda }=\mathrm{\Lambda }_0a^s`$ where $`\mathrm{\Lambda }_0`$,q, $`G_0`$ and s are constants. Now Eq.(12) can be written as,

$`\dot{\rho }+3{\displaystyle \frac{\dot{a}}{a}}{\displaystyle \frac{p}{c^2}}+{\displaystyle \frac{\dot{\mathrm{\Lambda }}c^2}{8\pi G}}=(\rho +\rho _\mathrm{\Lambda }){\displaystyle \frac{\dot{G}}{G}}+{\displaystyle \frac{3Kc\dot{c}}{4\pi Gc^2}}{\displaystyle \frac{2\mathrm{\Lambda }c\dot{c}}{8\pi G}}+{\displaystyle \frac{\mathrm{\Lambda }c^2\dot{G}}{8\pi G^2}}`$ (13)
Assuming conservation of ordinary matter, we put the left hand side and right hand side of Eq.(13) separately to zero. The underlying assumption being that the variations of $`\mathrm{\Lambda }`$, G and c are such that conservation of energy, as true with the non varying parameters, is still valid. The solution for left hand side of Eq.(13), being zero, is

$`\rho _\mathrm{\Lambda }={\displaystyle \frac{\mathrm{\Lambda }_0s(c_0)^2}{8\pi G_0}}{\displaystyle \frac{a(2n+sq)}{(2n+3\gamma +sq)}}+Ba^{3\gamma }`$ (14)
where B is a constant of integration. The right hand side of Eq.(13) can be written as,

$`{\displaystyle \frac{\mathrm{\Lambda }_0(c_0)^2}{8\pi G_0}}[{\displaystyle \frac{sq}{2n+3\gamma +sq}}2n]a^{2n+sq1}+{\displaystyle \frac{3K(c_0)^2n}{4\pi G_0}}a^{2nq3}qBa^{3\gamma 1}=0`$ (15)
A solution for this equation is

$`{\displaystyle \frac{sq}{2n+3\gamma +sq}}=2n,`$ (16)
$`2nq3=3\gamma 1,`$ (17)
and

$`{\displaystyle \frac{3K(c_0)^2n}{4\pi G_0}}=qB.`$ (18)
Using Eq.(17), Eq.(16) can be written as,

$`{\displaystyle \frac{qs}{s+2}}=2n.`$ (19)
Then $`q=\frac{3K(c_0)^2n}{4\pi G_0B}q_0n`$ and $`s=\frac{4}{q_02}`$ .

For the dust era ($`\gamma =1`$) Eq.(17) becomes

$`n={\displaystyle \frac{1}{q_02}}or4n=s`$ (20)
For n to be negative, as in the solution of the flatness problem, $`q_0<2`$. For the radiation dominated era ($`\gamma =\frac{4}{3}`$), Eq.(17) is

$`n={\displaystyle \frac{2}{q_02}}or2n=s`$ (21)
The Friedmann equation for a time varying cosmological parameter, Eq.(13), becomes,

$`{\displaystyle \frac{\dot{a}^2}{a^2}}={\displaystyle \frac{\mathrm{\Lambda }_0(c_0)^2}{3}}{\displaystyle \frac{(2n+3\gamma q)}{(2n+3\gamma +sq)}}a^{2n+s}+{\displaystyle \frac{8}{3}}\pi BG_0a^{q3\gamma }K(c_0)^2a^{2n2}`$ (22)
For the dust dominated universe, $`\gamma =1`$ , using Eq.(20)

$`{\displaystyle \frac{\dot{a}^2}{a^2}}={\displaystyle \frac{2\mathrm{\Lambda }_0(c_0)^2}{3(4n+2)}}a^{6n}+{\displaystyle \frac{8\pi BG_0}{3}}a^{2n2}K(c_0)^2a^{2n2}`$ (23)
For $`n<\frac{1}{2}`$ the cosmological term will go to zero at large times faster than the other two terms of Eq.(23). For $`n<1`$ the curvature term will tend to zero at large times. Thus for $`n<\frac{1}{2}`$ all the terms will vanish at large times solving both the cosmological and the flatness problems.

For the radiation dominated universe ($`\gamma =\frac{4}{3}`$ ), using equation (21)

$`{\displaystyle \frac{\dot{a}^2}{a^2}}={\displaystyle \frac{2\mathrm{\Lambda }_0(c_0)^2}{3(2n+2)}}a^{4n}+{\displaystyle \frac{8\pi BG_0}{3}}a^{2n2}K(c_0)^2a^{2n2}`$ (24)
For $`n<1`$ the $`\mathrm{\Lambda }`$ term will go to zero faster than the other two terms of the Eq.(24). As in the dust universe $`n<1`$ makes the curvature term vanish at large times. Thus in the radiation dominated universe $`n<1`$ solves both the cosmological and flatness problems.

We have solved the flatness and $`\mathrm{\Lambda }`$ problems in a Friedmann universe by assuming that the variation of c, G and $`\mathrm{\Lambda }`$ are such that the conservation of matter with fixed c, G and $`\mathrm{\Lambda }`$ still holds. In the absence of $`\mathrm{\Lambda }`$ the solution is the same as that without assuming energy conservation. With $`\mathrm{\Lambda }`$ we can still solve the cosmological problem but with different exponents. Thus it might be worth exploring a more fundamental theory that will allow the variation of the parameters c, G, $`\mathrm{\Lambda }`$ without violating energy conservation.

## Acknowledgements

PG thanks CSIR, NewDelhi for a research fellowship, and GVV thanks Prof. N. Dadhich for useful discussions and IUCAA, Pune for allowing to use their facilities.