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# 1 Introduction

## 1 Introduction

The Casimir problem for dielectrics - for general introductions see, for instance Refs. \[1-3\] - has turned out to be difficult to solve, in the presence of curved surfaces. The most typical example of a system of this sort is probably that of a single nonmagnetic compact spherical ball, surrounded by a vacuum. (Equivalently, one may imagine a spherical cavity in an otherwise uniform medium, thus dealing just with the situation typical for sonoluminescence.) Formally, in the presence of curved boundaries one is confronted with divergences when summing over all angular momenta up to infinity. This kind of divergence is usually absent when one deals with plane boundaries. Physically, the divergences are coming from the fact that phenomenological electrodynamics, implying use of the permittivity concept, becomes inappropriate at small distances. There exists a natural cutoff in the material, of the order of the intermolecular spacing, and in practice some kind of regularization has to be invoked in order to deal with the divergences in the formalism. More accurately this cutoff is the molecular diameter, as is most easily seen from the statistical mechanical method. By means of this method the electromagnetic Green function can be associated with the pair correlation function between dipole moments. The latter quantity is zero inside the hard cores, and its deviation from from the ”ideal” Green function extends typically a few molecular diameters outwards from the molecule.

In the case of nondispersive media, the use of zeta-function methods has proved to be very useful for force, or energy, calculations. The field theory approach to the Casimir problem has been considered at various places; in addition to the references above we may mention Refs. \[4-16\]. (This list is not intended to be complete; it covers mostly treatments of nonmagnetic media, and does not include the bulk of papers devoted to studies of the special case of media that satisfy the condition $`\epsilon \mu =1`$. A very extensive list of references is given in the recent report of Nesterenko et al. .) The Casimir energy $`E`$ calculated by field theoretical methods at zero temperature for a dilute nondispersive compact sphere of radius $`a`$ and refractive index $`n`$ is positive,

$$E=\frac{23}{384}\frac{\mathrm{}c}{\pi a}(n1)^2,$$
(1)
corresponding to an outward force.

Instead of making use of field theoretical methods for continuous matter, one may alternatively use quantum statistical mechanical methods. We shall in the first sections below consider methods that were developed by Høye and Stell, and others. Basic references to this kind of theory are  and . In the Casimir context, Høye and Brevik  used the quantum statistical mechanical path integral method to calculate the van der Waals force between dielectric plane plates. Recently, we have applied the same method to a single compact spherical ball . This statistical method, although probably not so well known as the field theoretical methods, turns out to be quite powerful. Thus, we can use it to calculate explicitly the short range terms in the single sphere’s free energy, and verify how the repulsive Casimir surface force as calculated by field theoretical methods is simply a residual, cutoff independent, term in a complicated expression containing many terms. Cf. in this context also Refs. , , and .

It is now natural to ask: what is the experimental status in this field? Recently, there has been an impressive improvement of the experimental accuracy as regards force measurements; one has been able to verify the theoretically predicted Casimir forces, lying in the piconewton range, up to an accuracy of about 1 per cent. In Ref.  the Casimir force was demonstrated between metallic surfaces of a sphere above a disk using a torsion pendulum, whereas in Refs. ,  an atomic force microscope was used.

One important lesson is to be learned from these experimental works is the following: they alway involve two (in principle there may even be more) bodies. The Casimir surface force on a single sphere is not measured. There seems not even to be an idea of how to measure such a force; probably this reflects simply that the force concept as such is not observationally well defined. Thus, in order to keep contact with experiments, at least in principle, one ought to consider at least two bodies. And this brings us to the theme of the present paper, namely to calculate the mutual free energy for a system of two spherically-shaped concentric nonmagnetic dielectrics. We will envisage that there is one compact sphere for $`r<a`$, and one semi-infinite similar medium for $`r>b`$, so that there is a vacuum gap of width $`d=ba`$ in between. There will be an attractive Casimir force between the two media. One may object that there is still no straightforward way to imagine measuring such a force; however this does not create difficulties for our main purpose, which is to calculate the Casimir force in a setting which maintains spherical symmetry and yet avoids the complications with internal, cutoff dependent, forces.

In the following four sections we shall deal with the quantum statistical mechanical theory, with an emphasis on the static limit (zero Matsubara frequency, where derivations are more simple). Thereafter, for comparison we consider the alternative field theoretical approach, limiting us for simplicity to the case of perfect metallic walls at $`r=a,b`$. The resulting expressions for the free energy are Eq. (18) for the static case (Matsubara frequency equal to zero) and Eq. (40) for the time-dependent case (general Matsubara frequency). These expressions are obtained within the statistical mechanical approach. Within the field theoretical approach, the finite-temperature free energy is given by Eq. (68) assuming, as mentioned, perfectly conducting walls.

There is one notable difference between the statistical mechanical approach and the field theoretical approach, as far as the free energy is concerned. In the first of these cases the method is basically more simple, at least in principle, as one needs only knowledge about the mode eigenvalues of the oscillating dipole moments in the dielectric medium; cf. Eq. (3). These eigenvalues are again related to the pair correlation function. In the second case the calculation is more indirect, as one first calculates the surface force (arising from the mutual interaction) on the outer surface implying use of Maxwell’s stress tensor, and thereafter relates the force to the free energy via integration of Eq. (67). That is, the field theoretical method involves use of the two-point functions for the electric and magnetic fields. As we also want to show that the results obtained by these widely different methods are in agreement, we consider some cases that are easy to analyse analytically, by both methods.

We ought to stress again the conceptual difference between the two methods studied in this paper. By the field theoretical method the Casimir effect is regarded as the energy shift due to the frequency eigenvalues of the quantized electromagnetic field in the presence of dielectric media. By the more recent statistical mechanical method this energy shift is regarded as a consequence of the dipole-dipole interaction between oscillating dipole moments embedded in the molecules of the media. The latter viewpoint can be realized by exploiting the analogue that exists between phonons in a solid, and electromagnetic waves or photons in vacuum. Then impurities in the solid will be the analogue to dielectric particles. These impurities will couple to the phonons of the solid and modify their frequencies. If, however, one wants to do the statistical mechanics of the latter system, e. g. to calculate its free energy, then one can first integrate out the coordinates of the pure solid that appear in the path integral representation of the quantized problem. With harmonic oscillators one encounters in this way Gaussian integrals which can easily be calculated. The result is independent of the impurities, except that interactions between them are introduced. Thus, the resulting change in free energy can be related to these induced induced interactions (being in general time-dependent) in the system of impurities. Likewise, in this picture the dipole-dipole interactions are related to the Casimir free energy.

We employ Gaussian electromagnetic units in this paper.

## 2 General remarks

Consider the free energy $`F(T)`$ due to the mutual interaction between two spherical dielectric bodies with concentric surfaces at $`r=a`$ and $`r=b`$. The attractive Casimir force between the surfaces, per unit area at the outer surface, is equal to $`f=1/(4\pi b^2)F/b`$. As shown earlier for the case of plates , this Casimir force can be interpreted as the dispersion force arising from thermal fluctuations of molecular dipole moments. By our quantum statistical mechanical considerations this also incorporates the quantum fluctuations at $`T=0`$. That means, all fluctuations can be regarded as purely thermal for any $`T`$. The difference between classical and quantum situations is that in the former case these fluctuations vanish at $`T=0`$ while in the latter case they remain finite. In  we considered the low density (or small $`\epsilon 1`$) version of the single-body problem showing, as mentioned above, that the divergences are due to the continuum model of the medium. A cutoff in length scale is needed. For realistic systems this cutoff is determined by the molecular hard cores through their influence upon the pair correlation function. For two polarizable particles the free energy due to their mutual attraction can be written as

$$\beta F=\frac{1}{2}\underset{n=1}{\overset{\mathrm{}}{}}\frac{1}{n}(\alpha _1\psi \alpha _2\psi )^n=\frac{1}{2}\mathrm{ln}(1\alpha _1\psi \alpha _2\psi ),$$
(2)
with $`\beta =1/k_BT`$. The $`\psi `$ represents the potential energy of the dipole-dipole interaction which for general $`K`$ (see Eq. (3) below) is given by Eqs. (6) and (7) below. Now the two particles can be generalized to and regarded to be our two spherical bodies, in the same way as two semi-infinite parallel plates were treated in . That means, the two spherical bodies are regarded as two particles with many internal degrees of freedom. In this way Eq. (2) becomes a short hand notation wherein $`\psi `$ represents the interaction between two points in the two bodies (over which we integrate), and the polarizabilities $`\alpha _1`$ and $`\alpha _2`$ become the respective internal correlation functions of the two bodies with their mutual interaction $`\psi `$ switched off. As noted in  the expression (2) is formally exact for coupled harmonic oscillators, i.e., the model that we are employing for the polarizable particles. In terms of graphs, the expression (2) represents the ring graphs in the $`\gamma `$ordering for the long-range forces, $`\gamma `$ being the inverse range of interaction . For coupled oscillators Eq. (2) above and Eq. (3) below are exact results .

Extending to the quantum mechanical case, Eq. (2) generalizes to

$$\beta F=\frac{1}{2}\underset{K}{}\mathrm{ln}(1\alpha _{1K}\psi _K\alpha _{2K}\psi _K),$$
(3)
where $`K=2\pi n/\beta `$ with $`n`$ integer (i.e., $`n\mathrm{},\mathrm{})`$. Note that $`K=\mathrm{}\zeta _n`$, where $`\zeta _n`$ is the Matsubara frequency $`\zeta _n=i\omega `$ and $`\omega `$ is the frequency.

For low density (or small $`\alpha `$) only the first term in the sum (2) is needed. This is the situation considered in  and found there, after some transformations, to be in agreement with earlier works. The first term means simply that one takes the (radiating) dipole interaction squared, average (integrate) over the fluctuating dipole moments, and finally integrate over the two media. Thus

$$F=\rho ^2𝑑𝐫_1𝑑𝐫_2\mathrm{\Phi },$$
(4)
where $`\rho `$ is the particle density, $`r_1<a,r_2>b`$, and

$$\beta \mathrm{\Phi }=\frac{3}{2}\underset{K}{}\alpha _K^2\left[2\psi _{DK}^2(r)+\psi _{\mathrm{\Delta }K}^2(r)\right],$$
(5)
where $`𝐫=𝐫_2𝐫_1`$. (Here $`𝐫_1`$ and $`𝐫_2`$ are positions in different media, so double counting does not occur.) The radiating dipole interactions used in (5) can be written as

$$\psi (12)=\psi _{DK}(r)D_K(12)+\psi _{\mathrm{\Delta }K}(r)\mathrm{\Delta }_K(12),$$
(6)
with

$`D_K(12)`$ $`=`$ $`3(\widehat{r}\widehat{a}_{1K})(\widehat{r}\widehat{a}_{2K})\widehat{a}_{1K}\widehat{a}_{2K},`$
$`\mathrm{\Delta }_K(12)`$ $`=`$ $`\widehat{a}_{1K}\widehat{a}_{2K}.`$
Here the hats denote unit vectors, and $`𝐚_{iK}`$ is the Fourier transform of the fluctuating dipole moment of particle number $`i`$ in imaginary time; cf. Eq. (5.2) in . Explicitly, from Eq. (5.10) in ,

$$\psi _{DK}(r)=\frac{e^\tau }{r^3}\left(1+\tau +\frac{1}{3}\tau ^2\right),$$

$$\psi _{\mathrm{\Delta }K}(r)=\frac{e^\tau }{r^3}\frac{2}{3}\tau ^2+\frac{4\pi }{3}\delta (𝐫),$$
(7)
with

$$\tau =\frac{i\omega r}{c}=\frac{Kr}{\mathrm{}c}\mathrm{for}\mathrm{}(\omega )<0(\text{or}K<0),$$

and $`K|K|`$ when extending to $`K>0`$ in (7) (see Eq. (5.11) in ).

For general $`K`$ we are not able to calculate the integral (4) in a direct way (but we can calculate it indirectly for arbitrary density, as will be argued later, in Sect. 4). We can integrate, however, for $`K=0`$. The integral of interest then becomes

$$I=_{r_1<a,r_2>b}𝑑𝐫_1𝑑𝐫_2\frac{1}{r^6},r^2=r_1^2+r_2^22r_1r_2\mathrm{cos}\theta .$$
(8)
This integral can be evaluated in closed form  (second reference). However, in Sect. 3 we want to extend this low density evaluation to the case of arbitrary density or arbitrary $`\epsilon `$. To do so, we need the contributions related to the various spherical harmonics. Thus we will here perform an expansion of the integral. This will also be used as an independent verification at the end of Sect. 4, where the more general theory developed there for arbitrary values of $`K`$ turns out to yield the correct result when $`K0`$.

Using spherical coordinates to integrate over the angle $`\theta `$ between $`𝐫_1`$ and $`𝐫_2`$ we first obtain ($`x=\mathrm{cos}\theta `$)

$`J={\displaystyle _1^1}{\displaystyle \frac{dx}{(r_1^2+r_2^2+2r_1r_2x)^3}}`$ $`=`$ $`{\displaystyle \frac{1}{4r_1r_2}}\left[{\displaystyle \frac{1}{(r_2r_1)^4}}{\displaystyle \frac{1}{(r_2+r_1)^4}}\right]`$ (9)
$`=`$ $`{\displaystyle \frac{1}{2r_1r_2^5}}{\displaystyle \underset{l=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{(2l+2)(2l+1)2l}{6}}\left({\displaystyle \frac{r_1}{r_2}}\right)^{2l1},`$
performing a series expansion to make it easy to relate to the result for high density. Then,

$$I=8\pi ^2_0^ar_1^2𝑑r_1_b^{\mathrm{}}r_2^2𝑑r_2J=\frac{8\pi ^2}{3}\underset{l=1}{\overset{\mathrm{}}{}}\frac{(l+1)l}{2l+1}\sigma _l,$$
(10)
with $`\sigma _l=(a/b)^{2l+1}`$.

Inserted in (4) we obtain ($`\alpha _0=\alpha `$)

$$\beta F=\beta \rho ^2\frac{3}{2}\alpha ^22I=\frac{1}{2}(\epsilon 1)^2\underset{l=1}{\overset{\mathrm{}}{}}\frac{(l+1)l}{2l+1}\sigma _l.$$
(11)
Note that for small $`\epsilon 1`$, Eq. (11) will be the high temperature result for which only $`K=0`$ contributes. This high temperature result at low density may in itself be of limited interest as it does not go beyond earlier results. But here we use it as a basis to make further developments. So in the next section the formalism is generalized to arbitrary density or $`\epsilon `$, although it is still restricted to $`K=0`$. In Sect. 4, a derivation that encompasses both arbitrary $`\epsilon `$ and $`K`$ is given.

## 3 The static case

For simplicity we first consider the static case, by which we mean that the frequency is zero ($`K=0`$). Then the electromagnetic dipole-dipole interaction is the well-known static, time-independent (also called instantaneous) one. By the time-dependent case we mean the general situation with $`K0`$. Then the dipole-dipole interaction will be the radiating or dynamical electromagnetic field where the time delay due to the finite speed of light is involved. Note that in general both the static and the dynamic cases contribute to the Casimir effect. The former, being proportional to $`T`$, contains the whole effect when $`T\mathrm{}`$, but vanishes when $`T0`$.

For general $`\epsilon `$ one should sum up the series in Eq. (2). This will not be a simple task. However, one can include a strength factor $`\lambda `$ along with the perturbing interaction $`\psi `$ and differentiate (2) (or (3)) to obtain

$$\beta \frac{F}{\lambda }|_{\lambda =1}=\psi (\alpha _1\psi _c\alpha _2),$$
(12)
where

$$\psi _c=\frac{\psi }{1\alpha _1\psi \alpha _2\psi }.$$

Here the $`\alpha _1\psi _c\alpha _2`$ will be the pair correlation function for the fluctuating dipole moments. As shown in Appendix A in  the $`\psi _c`$ (apart from a simple factor) is the Green function for the electromagnetic problem with the dielectric medium present while $`\psi `$ is the one for vacuum. Thus we can utilize Maxwell’s equations for electrostatics to obtain this zero frequency Green function or $`\psi _c`$ in the presence of two dielectric spheres.

The electrostatic potential $`\mathrm{\Phi }`$ fulfils the Laplace equation $`^2\mathrm{\Phi }=0`$ with $`\epsilon =`$const. Splitting off the spherical harmonic factor $`Y_{lm}=Y_{lm}(\theta ,\phi )`$,

$$\mathrm{\Phi }=\mathrm{\Phi }_l(r)Y_{lm}(\theta ,\phi ),$$
(13)
we can write the radially dependent term in the form

$`\mathrm{\Phi }=\{\begin{array}{cc}\frac{1}{\epsilon }\left(\frac{a}{r}\right)^{l+1}+B\left(\frac{r}{a}\right)^l,\hfill & r<a\hfill \\ C\left(\frac{a}{r}\right)^{l+1}+C_1\left(\frac{r}{a}\right)^l,\hfill & a<r<b\hfill \\ D\left(\frac{a}{r}\right)^{l+1},\hfill & b<r.\hfill \end{array}`$ (17)
From the boundary conditions the coefficients can be determined. We give the coefficient $`D`$ belonging to the exterior region

$$D=\frac{(2l+1)^2}{(\epsilon 1)^2(l+1)l}\frac{A_l}{(1A_l\sigma _l)},$$
(18)
where

$$A_l=\frac{(\epsilon 1)^2(l+1)l}{[\epsilon (l+1)+l](\epsilon l+l+1)}\text{and}\sigma _l=\left(\frac{a}{b}\right)^{2l+1}.$$
(19)
The coefficient $`D`$ represents the change of the field for $`r>b`$ relative to the $`\epsilon =1`$ case for a given point source. Via Eq. (12) the free energy is now obtained in a straightforward way. For small $`\epsilon 1`$ the quantity (12) is twice the quantity (11). Thus the expression (12) becomes

$$\beta \frac{F}{\lambda }|_{\lambda =1}=\underset{l=1}{\overset{\mathrm{}}{}}(2l+1)\frac{A_l\sigma _l}{1A_l\sigma _l}.$$
(20)
As we will argue below $`A_l\sigma _l`$ will be proportional to the strength factor squared, $`\lambda ^2`$. Thus integrating (17) we obtain the free energy

$$\beta F=\frac{1}{2}\underset{l=1}{\overset{\mathrm{}}{}}(2l+1)\mathrm{ln}(1A_l\sigma _l),$$
(21)
which clearly yields an attractive force between the two spherical bodies.

It should be noted that the series (18) is convergent as it contains no self-energy. From Eq. (16) it is seen that $`A_l1`$ and $`\sigma _l`$ decays like an exponential as $`l\mathrm{}`$, implying $`A_l\sigma _l<1`$. Further, no cutoff is needed as Eq. (18) only includes the free energy shift due to the mutual interaction between the two bodies. A ”self-energy” would arise if interactions within each body were considered. But yet the necessary minimum distance between molecules would prevent the latter expression from diverging .

## 4 Further analysis of the static case

The time-dependent case ($`K0`$) will be more complex to handle as we are not able to perform analytically the generalization of the integration (9) that gave the results (11) and (18). We find however that this case can be handled indirectly, noting that the quantity

$$M=\alpha _1\psi \alpha _2\psi $$
(22)
in Eqs. (2) and (12) can be regarded as a matrix. We want the trace of these expressions (as well as the expression (3)), which amounts to integrating over positions and dipolar moments of the particles. The matrix can be transformed into a diagonal matrix $`\mathrm{\Lambda }`$ through some matrix $`S`$,

$$M=S\mathrm{\Lambda }S^1.$$
(23)
Then

$$Tr(M^q)=Tr(\mathrm{\Lambda }^q)=\underset{i}{}\lambda _i^q,$$

where $`\lambda _i`$ are the diagonal elements of $`\mathrm{\Lambda }`$. Also,

$$(M^q)_{ij}=\underset{l}{}S_{il}(S^1)_{lj}\lambda _l^q.$$
(24)
Thus to obtain the free energy (2) or (3) we only need the eigenvalues $`\lambda _l`$. Use of the spherical harmonics $`Y_{lm}`$ for our present problem produces such a diagonalization and, as the results (17) and (18) show, the $`A_l\sigma _l`$ represent these eigenvalues. The prefactor $`2l+1`$ is simply the degeneracy factor.

However, without performing the integration (10) the identification of $`A_l\sigma _l`$ with the appropriate eigenvalues is not obvious and cannot be concluded from Eq. (15) alone. Then we turn to Eq. (12) and consider the correlation function (or the equivalent Green function) which can be expanded as

$$\alpha _1\psi _c\alpha _2=\frac{\alpha _1\psi \alpha _2}{1\alpha _1\psi \alpha _2\psi }=\alpha _1\psi \alpha _2\underset{n=0}{\overset{\mathrm{}}{}}M^n$$
(25)
with $`M=\alpha _1\psi \alpha _2\psi `$. Applying $`S`$ the $`M`$ is made diagonal such that

$$S^1\alpha _1\psi _c\alpha _2S=S^1\alpha _1\psi \alpha _2S\frac{1}{1\mathrm{\Lambda }},$$
(26)
and $`\mathrm{\Lambda }`$ or its eigenvalues $`\lambda _i`$ can be identified via the ratio

$$S^1\frac{\alpha _1\psi _c\alpha _2}{\alpha _1\psi \alpha _2}S=\frac{1}{1\mathrm{\Lambda }}.$$
(27)
Here the $`D`$ in Eq. (15) represents the numerator (the full correlation function), while the denominator can be identified with the first term in a chain bond expansion with one single potential bond $`\psi `$ and two hypervertices $`\alpha _1`$ and $`\alpha _2`$ (or correlation functions for the two media with their mutual interaction switched off). By chain bond expansion we mean the graphical representation of the terms in the expansion (22), where hypervertices $`\alpha _i`$ alternate with potential bonds $`\psi `$. This notation has its origin in the statistical mechanical theory of fluids . To go beyond standard mean field theory the Mayer graph expansion can be rearranged, and the chain bond will then become the leading correction (for forces of long range) to the correlation function of the reference system (e.g., hard spheres). In the present case with harmonic oscillators the expansion turns out to be exact for the pair correlations of amplitudes (corresponding to Gaussian fluctuations).

The first term of the expansion (22) is now obtained by considering the two spherical bodies separately, or equivalently by considering Eq. (14) first with $`a=0`$ and thereafter with $`b=\mathrm{}`$. Then there will be no multiple $`\psi `$ bonds going back and forth, as there are no longer two media present. First take away the inner sphere, which is done by putting $`a=0`$. Solving for $`D`$ one obtains ($`B=0`$)

$$D=D_0=\frac{2l+1}{\epsilon (l+1)+l}C.$$
(28)
The amplitude ratio $`D_0/C`$ will represent $`\alpha _2`$ (or $`\alpha _1`$). Secondly, take away the outer sphere, which is done by putting $`b=\mathrm{}`$. Solving for $`C`$ one then obtains ($`D=0,C_1=0`$)

$$C=C_{\mathrm{}}=\frac{2l+1}{\epsilon l+l+1}.$$
(29)
The amplitude ratio $`C_{\mathrm{}}/(1/\epsilon )`$ (see Eq. (14)) will represent $`\alpha _1`$ (or $`\alpha _2`$). Thus $`D_0`$ will represent $`\alpha _1\psi \alpha _2`$ as $`\psi `$ is represented by $`1/\epsilon `$. Likewise the $`D`$ as given by Eq. (15) represents the full correlation (or Green) function as both spheres are present, by which the ratio $`D/D_0`$ yields the sought eigenvalues of Eq. (24).

Combining Eqs. (25) and (26),

$$D_0=\frac{(2l+1)^2}{[\epsilon (l+1)+l](\epsilon l+l+1)}.$$
(30)
Relating this to Eqs. (15) and (24) we see that the eigenvalues of $`\mathrm{\Lambda }`$ are $`\lambda _l=A_l\sigma _l,D/D_0=1/(1\lambda _l)`$. Thus we recover the results (17) and (18) when $`\lambda _l`$ is used in the expressions (12) and (2), taking into account the degeneracy factor $`2l+1`$. That means, the present indirect approach is fully consistent with the explicit integration (10) that led to the same results.

## 5 The time-dependent case

Including the time dependence the solutions of Maxwell’s equations become more complex. One has to solve the vector wave equation, and the fields have to satisfy the boundary conditions at the two surfaces. Again the spherical harmonics $`Y_{lm}`$ can be used, and the remaining problem how to decompose the vector fields parallel and transverse to the spherical surfaces is conveniently dealt with in terms of the TM (transverse magnetic) and TE (transverse electric) mode . Application of the angular momentum operator $`𝐋=(1/i)𝐫\times `$ (with $`\mathrm{}=1`$) creates a vector normal to $`𝐫`$, i. e. $`𝐫𝐋=0`$, and is thus parallel to the spherical surfaces. As $`𝐋`$ commutes with the $`^2`$ operator of the wave equation, and as $`𝐋`$ does not contain differentiation with respect to $`r`$, the wave equation has TM solutions of the form

$$𝐁=\frac{\mathrm{\Phi }(r)}{r}𝐋Y_{lm},$$
(31)
where $`\mathrm{\Phi }(r)`$ is some function of $`r`$. Likewise the TE solutions follow with $`𝐁`$ replaced by $`𝐄`$.

The $`𝐄`$ field is now obtained from

$$\times 𝐁=\frac{\epsilon }{c}\frac{𝐄}{t}=ik\epsilon 𝐄,$$
(32)
where $`k=\omega /c`$. Thus we need the formula

$$i\times 𝐋=𝐫^2(1+r\frac{}{r}).$$
(33)
Now applying boundary conditions on the spherical surfaces, we find that the condition on the radial component of $`𝐄`$ coincides with that of $`𝐁`$, so that we need its component $`𝐄_{}`$ transverse to $`𝐫`$ which comes from the last term in (30) where only derivatives with respect to the polar angles are needed from the $``$ operator. The latter again act only on $`Y_{lm}`$ which are the same on both sides of the interfaces and can thus be disregarded as far as boundary conditions are concerned. Therefore we are left with the $`r`$-dependence of $`𝐄`$ , where the term of interest is given by

$$(1+r\frac{d}{dr})(\frac{\mathrm{\Phi }(r)}{r})=\frac{d\mathrm{\Phi }(r)}{dr}.$$
(34)
The solutions of the wave equation for a given frequency are the Riccati-Bessel functions. As independent pair of functions it is convenient to choose the functions that are proportional to $`rj_l(kr)`$ and to $`rh_l^{(1)}(kr)`$; the first one because of its finiteness at the origin, the second because of outgoing boundary conditions at infinity. After frequency rotation, and convenient normalization, these are the functions denoted by $`s_l`$ and $`e_l`$ in the field theory section below, in Eq. (53). For simplicity we will in the present section omit the subscript $`l`$. We will let subscripts $`a,b`$ refer to functions taken at $`r=a,b`$, and add an extra subscript $`\epsilon `$ to indicate that the function is taken inside a dielectric medium. Like Eq. (14) we can now write

$`\mathrm{\Phi }(r)=\{\begin{array}{cc}e_\epsilon +Bs_\epsilon ,\hfill & r<a\hfill \\ Ce+C_1s,\hfill & a<r<b\hfill \\ De_\epsilon ,\hfill & b<r.\hfill \end{array}`$ (38)
As compared to Eq. (14) the coefficient $`1/\epsilon `$ for $`r<a`$ has been dropped since the $`\mathrm{\Phi }(r)`$ represents the magnetic field, but has no further consequence as it only affects the other coefficients by a proportionality factor $`\epsilon `$. Requiring continuity of the tangential components $`𝐁_{}`$ and $`𝐄_{}`$ across the surfaces we obtain the equations

$$e_{a\epsilon }+Bs_{a\epsilon }=Ce_a+C_1s_a,$$

$$\frac{1}{\epsilon }(e_{a\epsilon }^{}+Bs_{a\epsilon }^{})=Ce_a^{}+C_1s_a^{},$$

$$Ce_b+C_1s_b=De_{b\epsilon },$$

$$Ce_b^{}+C_1s_b^{}=\frac{D}{\epsilon }e_{b\epsilon }^{},$$
(39)
where we emphasize that the primes here mean differentiation with respect to $`r`$.

To obtain the eigenvalues of interest we now proceed as in Sect. 4. So like Eq. (25) we find from the two last members of Eq. (33) (i. e., $`a=0`$)

$$D=D_0=c_2C,\text{with}c_2=\epsilon \frac{e_bs_b^{}e_b^{}s_b}{\epsilon e_{b\epsilon }s_b^{}e_{b\epsilon }^{}s_b},$$
(40)
and like Eq. (26) we find from the two first members of Eq. (33) (i. e., $`b=\mathrm{}`$ and $`C_1=0`$)

$$C=C_{\mathrm{}}=c_1,\text{with}c_1=\frac{e_{a\epsilon }^{}s_{aϵ}e_{a\epsilon }s_{a\epsilon }^{}}{\epsilon e_a^{}s_{a\epsilon }e_as_{a\epsilon }^{}}.$$
(41)
Combining these we obtain, like Eq. (27),

$$D_0=c_1c_2.$$
(42)
As explained below Eq. (24) and in connection with Eqs. (25) and (26), this $`D_0`$ represents the chain with a single potential bond $`\psi `$. The full chain bond (see explanation below Eq. (24)) will be obtained by solving Eqs. (33) as they stand. This yields

$$D=\frac{D_0}{1\lambda _{\epsilon l}},$$
(43)
where

$$\lambda _{\epsilon l}=\frac{(\epsilon s_a^{}s_{a\epsilon }s_as_{a\epsilon }^{})(\epsilon e_b^{}e_{b\epsilon }e_be_{b\epsilon }^{})}{(\epsilon e_a^{}s_{a\epsilon }e_as_{a\epsilon }^{})(\epsilon e_{b\epsilon }s_b^{}e_{b\epsilon }^{}s_b)}$$
(44)
are the eigenvalues of interest in the construction of the free energy; cf. the argument above Eq. (27) in Sect. 4.

The static case ($`\omega =0`$) is recovered by putting $`e_\epsilon =e=1/r^l`$ and $`s_\epsilon =s=r^{l+1}`$, which yields $`\lambda _{\epsilon l}=A_l\sigma _l`$ in accordance with Eq. (15). Note that Eqs. (33) are somewhat different from those used in the static case as $`\epsilon `$ is replaced by $`1/\epsilon `$ while $`l`$ and $`l+1`$ are interchanged, but the result is the same.

When $`\omega 0`$ there is also another set of modes, namely the TE modes. They are obtained by replacing $`𝐁`$ with $`𝐄`$ in Eq. (28), and by interchanging $`𝐁`$ and $`𝐄`$ in Eq. (29) while removing the factor $`\epsilon `$ and the minus sign on the right hand side. Again imposing boundary conditions, Eqs. (33) are recovered, except that the factor $`1/\epsilon `$ is no longer present. Solving for $`D`$ we recover the results (34)-(38) also, except that all factors $`\epsilon `$ are no longer present. The eigenvalues of interest now become

$$\lambda _l=\frac{(s_a^{}s_{a\epsilon }s_as_{a\epsilon }^{})(e_b^{}e_{b\epsilon }e_be_{b\epsilon }^{})}{(e_a^{}s_{a\epsilon }e_as_{a\epsilon }^{})(e_{b\epsilon }s_b^{}e_{b\epsilon }^{}s_b)}.$$
(45)
With the eigenvalues (38) and (39), the expression (18) for the free energy can be extended in a straightforward way to the time-dependent case, and we get

$$\beta F=\frac{1}{2}\underset{K}{}\underset{l=1}{\overset{\mathrm{}}{}}(2l+1)[\mathrm{ln}(1\lambda _{ϵl})+\mathrm{ln}(1\lambda _l)],$$
(46)
where the prefactor $`2l+1`$ is again the degeneracy factor, and $`K=2\pi n/\beta `$ with $`n`$ integer (i.e., $`n\mathrm{},\mathrm{}`$).

Finally it can be noted that for two parallel plates separated by a distance $`d`$ the free energy can be written in a similar general form. This energy can be found by integrating the surface force given by Eq. (2.9) of Ref. . This surface force is the famous Lifshitz result . The parallel plates result for the mutual free energy per unit area becomes

$$\beta F=\frac{1}{4\pi }\underset{K}{}_{\zeta _n/c}^{\mathrm{}}\left[\mathrm{ln}(1\lambda _{\epsilon q})+\mathrm{ln}(1\lambda _q)\right]q𝑑q,$$
(47)
where

$$\lambda _{\epsilon q}=A_ne^{2qd},\lambda _q=B_ne^{2qd},$$

with

$$A_n=\left(\frac{\epsilon \kappa }{\epsilon +\kappa }\right)^2,B_n=\left(\frac{1\kappa }{1+\kappa }\right)^2,$$

$$\kappa =\left[1(\epsilon 1)\left(\frac{\omega }{cq}\right)^2\right]^{1/2},K=i\mathrm{}\omega =\mathrm{}\zeta _n=2\pi n/\beta .$$

It should be noted that Eqs. (40) and (41) are general results, valid for arbitrary permittivity $`\epsilon (\omega )`$ and temperature, and they give the free energy due to the mutual interaction between the two media. There are no diverging self-energy terms. From Eq. (37) one must expect $`\lambda _{\epsilon l},\lambda _l<1`$, and in the $`K=0`$ case (18) one has the converging factor $`\sigma _l=(a/b)^{2l+1}`$. This convergence will not be weakened when $`K0`$ as then exponential factors also enter the solution of the wave equation for imaginary frequency.

## 6 Field-theoretical approach: the surface force

We now consider, as an alternative, the field theoretical approach to the same physical system, with the simplification, however, that the compact media are perfect conductors ($`\epsilon =\mathrm{}`$). Thus we can compare with the above general result in this special case. We shall make use of the local Green-function method, as developed in particular by Schwinger and his school. A basic reference to this kind of theory applied to the case of spherical symmetry (a perfecly conducting shell) is Milton et al. . To our knowledge Milton was also the first to apply this theory to the compact ball problem . Generalization of the theory, so as to take into account electrostriction, was made by Brevik . Later references are - and . (This list does not include the main part of the references dealing with $`\epsilon \mu =1`$ media, as well as papers dealing with the mode summation method.) We now put $`\mathrm{}=c=k_B=1`$.

Once the assumption about perfect conductors is accepted, the formalism becomes relatively simple. Since all fields in the regions $`r<a`$ and $`r>b`$ are equal to zero, we have to consider the fields in the vacuum gap only. The Green function $`𝚪(x,x^{})`$ for two spacetime points $`x`$ and $`x^{}`$ has a Fourier transform $`𝚪(𝐫,𝐫^{},\omega )`$ defined by

$$𝚪(x,x^{})=_{\mathrm{}}^{\mathrm{}}\frac{d\omega }{2\pi }e^{i\omega \tau }𝚪(𝐫,𝐫^{},\omega ),$$
(48)
with $`\tau =tt^{}`$. Note that the convention of Fourier transform used here implies a change of sign of $`\omega `$ (i. e., $`\omega \omega `$), compared to the definition used in the preceding sections, e. g. Eq. (7). The governing equation for $`𝚪`$, as following from Maxwell’s equations, is

$$\times \times 𝚪(𝐫,𝐫^{},\omega )\omega ^2𝚪(𝐫,𝐫^{},\omega )=\omega ^2\mathrm{𝟏}\delta (𝐫𝐫^{}),$$
(49)
and the spectral two-point function for the electric field components is

$$iE_i(𝐫)E_k(𝐫^{})_\omega =(4\pi )\mathrm{\Gamma }_{ik}(𝐫,𝐫^{},\omega )$$
(50)
(the prefactor $`4\pi `$ appearing because of our present use of the Gaussian system of units). There are two scalar Green functions, $`F_l(r,r^{})`$ and $`G_l(r,r^{})`$, since there are two independent field modes. The connection between these functions and the spectral two-point functions is

$$iE_r(r)E_r(r^{})_\omega =\frac{(4\pi )}{rr^{}}\underset{l=1}{\overset{\mathrm{}}{}}\frac{2l+1}{4\pi }l(l+1)G_l(r,r^{}),$$
(51)
$$iE_{}(r)E_{}(r^{})_\omega =(4\pi )\underset{l=1}{\overset{\mathrm{}}{}}\frac{2l+1}{4\pi }[\omega ^2F_l(r,r^{})+\frac{1}{rr^{}}\frac{}{r}r\frac{}{r^{}}r^{}G_l(r,r^{})],$$
(52)
$$iH_r(r)H_r(r^{})_\omega =\frac{(4\pi )}{rr^{}}\underset{l=1}{\overset{\mathrm{}}{}}\frac{2l+1}{4\pi }l(l+1)F_l(r,r^{}),$$
(53)
$$iH_{}(r)H_{}(r^{})_\omega =(4\pi )\underset{l=1}{\overset{\mathrm{}}{}}[\omega ^2G_l(r,r^{})+\frac{1}{rr^{}}\frac{}{r}r\frac{}{r^{}}r^{}F_l(r,r^{})].$$
(54)
Here, it is assumed that the vectors $`𝐫`$ and $`𝐫^{}`$ lie in the same angular direction. The radial difference $`rr^{}`$, however, does not have to be small.

For simplicity we shall denote the scalar Green functions generically by $`\mathrm{\Delta }_l(r,r^{})`$ (thus $`\mathrm{\Delta }_l`$ is either $`F_l`$ or $`G_l`$). Their governing equation is

$$\left[\frac{^2}{r^2}+\frac{2}{r}\frac{}{r}+\omega ^2\frac{l(l+1)}{r^2}\right]\mathrm{\Delta }_l(r,r^{})=\frac{1}{r^2}\delta (rr^{}).$$
(55)
The solution contains spherical Bessel functions, and has the general form

$$\mathrm{\Delta }_l(r,r^{})=\frac{ik}{1\stackrel{~}{C}_I\stackrel{~}{C}_{II}}\left[j_l(kr_<)\stackrel{~}{C}_Ih_l^{(1)}(kr_<)\right]\left[h_l^{(1)}(kr_>)\stackrel{~}{C}_{II}j_l(kr_>)\right],$$
(56)
where $`k=|\omega |`$, $`\stackrel{~}{C}_I\mathrm{and}\stackrel{~}{C}_{II}`$ being constants. This form satisfies the discontinuity condition following from Eq. (49) on the radial derivative of $`\mathrm{\Delta }_l`$ at $`r=r^{}`$, with the Wronskian $`W\{j_l(x),h_l^{(1)}(x)\}=i/x^2`$. Taking into account the boundary conditions at $`r=a,b`$ we can determine the constants: for the F (or TE) mode we get

$$\stackrel{~}{C}_{IF}(ka)=\frac{\stackrel{~}{s}_l(ka)}{\stackrel{~}{e}(ka)},\stackrel{~}{C}_{IIF}(kb)=\frac{\stackrel{~}{e}_l(kb)}{\stackrel{~}{s}_l(kb)},$$
(57)
whereas for the G (or TM) mode

$$\stackrel{~}{C}_{IG}(ka)=\frac{\stackrel{~}{s}_l^{}(ka)}{\stackrel{~}{e}_l^{}(ka)},\stackrel{~}{C}_{IIG}(kb)=\frac{\stackrel{~}{e}_l^{}(kb)}{\stackrel{~}{s}_l^{}(kb)}.$$
(58)
Here, we let prime mean differentiation with respect to the whole argument. We now perform a complex frequency rotation, $`\omega i\widehat{\omega },ki|\widehat{\omega }|=i\widehat{k}`$, and replace the conventional Riccati-Bessel functions $`\stackrel{~}{s}_l(x)=xj_l(x),\stackrel{~}{e}_l(x)=xh_l^{(1)}(x)`$ by new ones $`s_l,e_l`$ defined according to

$$s_l(x)=(i)^{l+1}\stackrel{~}{s}_l(ix)=\sqrt{\frac{\pi x}{2}}I_\nu (x),$$

$$e_l(x)=i^{l+1}\stackrel{~}{e}_l(ix)=\sqrt{\frac{2x}{\pi }}K_\nu (x).$$
(59)
Here $`\nu =l+1/2,I_\nu `$ and $`K_\nu `$ are modified Bessel functions, and the Wronskian of importance now is $`W\{s_l,e_l\}=1`$. The frequency rotation implies that we replace the ”tilde” constants $`\stackrel{~}{C}`$ by new constants $`C`$, in accordance with the relation $`\stackrel{~}{C}(ix)=(1)^{l+1}C(x)`$. Explicitly,

$$C_{IF}(x)=\frac{s_l(x)}{e_l(x)},C_{IIF}(y)=\frac{e_l(y)}{s_l(y)},$$

$$C_{IG}(x)=\frac{s_l^{}(x)}{e_l^{}(x)},C_{IIG}(y)=\frac{e_l^{}(y)}{s_l^{}(y)},$$
(60)
where we here and henceforth let $`x`$ and $`y`$ be defined by $`x=\widehat{k}a,y=\widehat{k}b`$.

We now return to the expansions (45)-(48) for the spectral two-point functions. Of main interest for us are these functions when the points $`𝐫`$ and $`𝐫^{}`$ are close to each other, but not overlapping. We moreover set the time-splitting parameter $`\tau =tt^{}`$ equal to zero. Substituting the two-point functions in Maxwell’s stress tensor we can calculate the surface force density on either of the two surfaces. We choose the outer surface $`r=b`$, since it will then become easy to relate the force to the free energy. Writing for simplicity $`E_r^2(r)`$ instead of $`E_r(r)E_r(r^{})_{r^{}r}`$, we obtain for $`T=0`$ the various two-point functions at $`r=b`$:

$$E_r^2(b)=\frac{(4\pi )}{\pi b^4}_0^{\mathrm{}}\frac{dy}{y}\underset{l=1}{\overset{\mathrm{}}{}}\frac{2l+1}{4\pi }l(l+1)\frac{s_l(y)C_{IG}(x)e_l(y)}{s_l^{}(y)C_{IG}(x)e_l^{}(y)},$$
(61)
$$E_{}^2(b)=H_r^2(b)=0,$$
(62)
$$H_{}^2(b)=\frac{(4\pi )}{\pi b^4}_0^{\mathrm{}}y𝑑y\underset{l=1}{\overset{\mathrm{}}{}}\frac{2l+1}{4\pi }[\frac{s_l(y)C_{IG}(x)e_l(y)}{s_l^{}(y)C_{IG}(x)e_l^{}(y)}+\frac{s_l^{}(y)C_{IF}(x)e_l^{}(y)}{s_l(y)C_{IF}(x)e_l(y)}]$$
(63)
(the prefactors $`4\pi `$ again reflecting the Gaussian units).

Using Maxwell’s stress tensor we can write the surface force density on the outer surface as

$$f_b=\frac{1}{8\pi }E_r^2(b)+\frac{1}{8\pi }H_{}^2(b).$$
(64)
Substituting Eqs. (55) and (57) into Eq. (58) we obtain, when taking into account the governing equation for the Riccati-Bessel functions,

$$s_l^{\prime \prime }(y)=(1+l(l+1)/y^2)s_l(y)$$
(65)
(and similarly for $`e_l(y)`$), that

$$f_b=\frac{1}{2\pi b^4}_0^{\mathrm{}}y𝑑y\underset{l=1}{\overset{\mathrm{}}{}}\frac{2l+1}{4\pi }[\frac{s_l^{}(y)C_{IF}(x)e_l^{}(y)}{s_l(y)C_{IF}(x)e_l(y)}+\frac{s_l^{\prime \prime }(y)C_{IG}(x)e_l^{\prime \prime }(y)}{s_l^{}(y)C_{IG}(x)e_l^{}(y)}].$$
(66)
From this expression it is apparent how both modes F and G contribute to the force.

We can write Eq. (60) as a sum of the following two terms:

$$f_b=f_b^{(0)}+f_b^{int},$$
(67)
where

$$f_b^{(0)}=\frac{1}{2\pi b^4}_0^{\mathrm{}}y𝑑y\underset{l=1}{\overset{\mathrm{}}{}}\frac{2l+1}{4\pi }[\frac{s_l^{}(y)}{s_l(y)}+\frac{s_l^{\prime \prime }(y)}{s_l^{}(y)}],$$
(68)
$$f_b^{int}=\frac{1}{2\pi b^2}_0^{\mathrm{}}𝑑\widehat{k}\underset{l=1}{\overset{\mathrm{}}{}}\frac{2l+1}{4\pi }\frac{}{b}\mathrm{ln}\{[1\frac{s_l(x)}{e_l(x)}\frac{e_l(y)}{s_l(y)}][1\frac{s_l^{}(x)}{e_l^{}(x)}\frac{e_l^{}(y)}{s_l^{}(y)}]\},$$
(69)
with $`y=\widehat{k}b`$ (the operator $`/b`$ is taken at constant value of $`a`$). The expression (62) is the same as the inner contribution to the surface force on a perfectly conducting shell . This term does not involve the interaction between the two media, and will be discarded in the following. Of interest for us is the interaction term (63). As $`s_l(y)=\frac{1}{2}e^y`$ and $`e_l(y)=e^y`$ for large $`y`$, it is evident from (63) that $`f_b0`$ if the outer surface recedes to infinity while the inner surface is kept constant. This is physically as it should be.

A remark is here in order, concerning the physical meaning of the two force terms in Eq. (61), in particular the possibility of making measurements. It ought to be emphasized, first of all, that the term $`f_b^{(0)}`$ is a mathematical construct. It does not seem to be possible to measure this term, not even in principle. If one imagines the case of a perfectly conducting singular shell with radius $`a`$, the case studied in  and also in , then $`f_b^{(0)}`$ has to be taken together with a similar term on the outside to make up a surface force that in principle ought to be measurable. However, as far as we know, no measurement has so far been made for even such a complete shell. In our case, what is measurable, at least in principle, is the interaction term (63). For instance, one might envisage to measure the attractive force between a micrometer-sized conducting sphere and a semi-spherical trough in a conducting plate, thus some kind of generalization of the atomic force microscope measurements reported in  and .

The expressions above refer to zero temperature. The transition to finite temperatures is made by means of a discretization of the frequencies,

$$\widehat{k}K=2\pi n/\beta ,xKa,$$
(70)
with $`n`$ an integer. The rule for going from frequency integral to a sum over Matsubara frequencies is

$$_0^{\mathrm{}}𝑑\widehat{k}\frac{2\pi }{\beta }\underset{n=0}{\overset{\mathrm{}}{}}^{},$$
(71)
where the prime on the summation sign means that the $`n=0`$ term is taken with half weight. The finite-temperature force expression accordingly becomes (recall that $`\nu =l+1/2`$)

$$f_b^{int}=\frac{1}{2\pi b^2\beta }\underset{n=0}{\overset{\mathrm{}}{}}^{}\underset{l=1}{\overset{\mathrm{}}{}}\nu \frac{}{b}\mathrm{ln}\{[1\frac{s_l(x)}{e_l(x)}\frac{e_l(y)}{s_l(y)}][1\frac{s_l^{}(x)}{e_l^{}(x)}\frac{e_l^{}(y)}{s_l^{}(y)}]\},$$
(72)
where now $`x=2\pi na/\beta `$, $`y=2\pi nb/\beta `$.

As for measurements of a force like $`f_b^{int}`$ there are subtle problems although the free energy (Eq. (68) below) is well defined. One may imagine that the two spherical media are liquids, and that the outer spherical shell can move. (The inner shell can also move if liquid is added or removed through a small pipe.) However, there is an extra complication compared to the case of parallel plates, namely the change of radius of a spherical surface. This will change the free energy associated with the surface tension. Although the latter change of energy is finite, a more precise evaluation of it will obviously be a complex task. The molecular structure has to be taken into account at the surface where the density changes abruptly.

It can be noted, however, that the sum of the two surface energies must be the opposite of the general result (40) for $`a=b`$, i. e., with the two spherical surfaces fused together. One is then left with no surfaces at all, and the bulk free energy applies everywhere. However, simply putting $`a=b`$ in a continuum approach does not work; Eq. (40) will diverge unless a cutoff is introduced for large $`l`$ to mimic the molecular diameter. Whether the self-force $`f_b^{(0)}`$ in Eq. (62) is possibly related to such a surface tension energy or not is a problem that we have so far not been able to clear up.

## 7 The free energy, analytically and numerically

Since we have calculated the force density on the outer surface due to the mutual interaction, it is easy to derive the corresponding expression for the interaction free energy $`F^{int}`$. We imagine the outer surface to be displaced by a small amount $`db`$, while the inner surface is kept constant. The relation

$$f_b^{int}=\frac{1}{4\pi b^2}\frac{F^{int}}{b}$$
(73)
is integrated from $`b`$ to infinity, noting that $`F^{int}=0`$ at $`b=\mathrm{}`$. Making use of (66) we thus obtain, dropping the superscript ’int’,

$$\beta F=2\underset{n=0}{\overset{\mathrm{}}{}}^{}\underset{l=1}{\overset{\mathrm{}}{}}\nu \mathrm{ln}\{[1\frac{s_l(x)}{e_l(x)}\frac{e_l(y)}{s_l(y)}][1\frac{s_l^{}(x)}{e_l^{}(x)}\frac{e_l^{}(y)}{s_l^{}(y)}]\},$$
(74)
valid at arbitrary temperatures. Comparing with the more general result of Eqs. (38)-(40) in Sect. 5 one finds that Eq. (68) agrees with these when $`\epsilon \mathrm{}`$ as then $`\epsilon s_a^{}s_{a\epsilon }s_as_{a\epsilon }^{},s_a^{}s_{a\epsilon }s_as_{a\epsilon }^{}`$, etc. (with $`s_a=s_l(x)`$ etc. as introduced above Eq. (32)).

At $`T=0`$, where the free energy $`F`$ is the same as the energy $`E`$, we can write

$$E=\frac{1}{\pi a}_0^{\mathrm{}}𝑑x\underset{l=1}{\overset{\mathrm{}}{}}\nu \mathrm{ln}\{[1\frac{s_l(x)}{e_l(x)}\frac{e_l(y)}{s_l(y)}][1\frac{s_l^{}(x)}{e_l^{}(x)}\frac{e_l^{}(y)}{s_l^{}(y)}]\}.$$
(75)
Expressions (68) and (69) hold for arbitrary widths of the annular region. It is of interest, before embarking on numerical evaluations, to analyse some limiting cases by analytical means. The limiting case of immediate interest is that of a narrow slit, i.e.,

$$\xi \frac{ba}{a}1.$$
(76)
This case is motivated physically from the fact that the Casimir measurements are made for small separations only, and also because we have in this way the possibility to check our results against the standard results for parallel plates in the limit when $`\xi 0`$.

At $`T=0`$ we find, when $`x`$ and $`y`$ lie close to each other ,

$$\frac{s_l(x)}{e_l(x)}\frac{e_l(y)}{s_l(y)}=\frac{s_l^{}(x)}{e_l^{}(x)}\frac{e_l^{}(y)}{s_l^{}(y)}=e^{\nu \varphi },$$
(77)
to $`O(1/\nu )`$ in the uniform asymptotic (or Debye) expansion. Here

$$\varphi =2\xi \sqrt{1+z^2}[1\frac{1}{2}\frac{\xi }{1+z^2}+\mathrm{}],z=\frac{x}{\nu }.$$
(78)
Keeping only the first term, we find the $`T=0`$ interaction energy to be

$$E=\frac{2}{\pi a}\underset{l=1}{\overset{\mathrm{}}{}}\nu ^2_0^{\mathrm{}}𝑑z\mathrm{ln}(1e^{2\xi \nu \sqrt{1+z^2}}).$$
(79)
This expression can be processed further, if we make a power expansion of the logarithm and take into account the property $`_{l=1}^{\mathrm{}}\nu ^2e^{\nu \varphi }2/\varphi ^3`$ when $`\varphi 0`$ . Then,

$$E=\frac{1}{2\pi a\xi ^3}\zeta (4)_0^{\mathrm{}}\frac{dz}{(1+z^2)^{3/2}}=\frac{\pi ^3}{180a}\frac{1}{\xi ^3},$$
(80)
which corresponds to the following interaction energy per unit surface (total surface area $`A=4\pi a^2`$, and $`d=ba`$):

$$\frac{E}{A}=\frac{\pi ^2}{720}\frac{1}{d^3}.$$
(81)
This simple calculation thus provides us with a satisfactory check: Eq. (75) is the conventional expression for the Casimir energy of two parallel plates. (The expression includes the effect of retardation. That is, the distance $`d`$ is much larger than the characteristic wavelength of the absorption spectrum of the medium.) Thus, by retaining the first order term in $`\xi `$ we see that our theory reduces to the standard $`T=0`$ theory. Corrections to the theory arising from the curvature of the surfaces can in principle be worked out by going to larger powers in $`\xi `$.

At finite temperatures, we obtain for the free energy

$$\beta F=4\underset{n=0}{\overset{\mathrm{}}{}}^{}\underset{l=1}{\overset{\mathrm{}}{}}\nu \mathrm{ln}(1e^{2\xi \sqrt{\nu ^2+n^2t^2}}),t=2\pi a/\beta .$$
(82)
This expression, as before, implies keeping of only the first term in the expansion (72), but it puts no restriction on the temperature.

Let us consider the limiting case of high temperatures, first going back to the expression (68), holding for arbitrary widths $`d`$. For the highest temperatures (classical limit), only the lowest Matsubara frequency ($`n=0`$) contributes. As $`x=nt,y=bnt/a`$, it is seen that we then need to evaluate $`s_l`$ and $`e_l`$ when the arguments tend to zero. As

$$s_l(x)=\frac{\sqrt{\pi }}{\mathrm{\Gamma }(\nu +1)}(\frac{x}{2})^{(\nu +\frac{1}{2})},e_l(x)=\frac{\mathrm{\Gamma }(\nu )}{\sqrt{\pi }}(\frac{x}{2})^{(\nu +\frac{1}{2})}$$
(83)
for small arguments, we have

$$\frac{s_l(x)}{e_l(x)}\frac{e_l(y)}{s_l(y)}=\frac{s_l^{}(x)}{e_l^{}(x)}\frac{e_l^{}(y)}{s_l^{}(y)}=(\frac{a}{b})^{2l+1},$$
(84)
so that the contribution from $`n=0`$ becomes

$$\beta F(n=0)=\underset{l=1}{\overset{\mathrm{}}{}}(2l+1)\mathrm{ln}[1(\frac{a}{b})^{2l+1}].$$
(85)
This is in agreement with our previus expression (18) ($`A_l=1`$ when $`\epsilon \mathrm{}`$), except from a factor 2. The physical reason for this is that both F and G modes contribute to Eq. (79), whereas only one mode contributes in (18). This artifact in Eq. (79) is related to the fact that $`\epsilon =\mathrm{}`$ is considered, while in Eq. (18) $`\omega =0`$ is considered before the limit $`\epsilon \mathrm{}`$ is taken.

In the case of a narrow slit we obtain from (76) the $`n=0`$ contribution

$$\beta F(n=0)=2\underset{l=1}{\overset{\mathrm{}}{}}\nu \mathrm{ln}(1e^{2\xi \nu }).$$
(86)
Again making a power expansion of the logarithm, and observing the relationship $`_{l=1}^{\mathrm{}}\nu e^{\nu \varphi }=1/\varphi ^2`$ when $`\varphi 0`$, we get

$$\beta F(n=0)=\frac{\zeta (3)}{2}\frac{1}{\xi ^2},$$
(87)
which corresponds to

$$\frac{\beta F(n=0)}{A}=\frac{\zeta (3)}{8\pi }\frac{1}{d^2}.$$
(88)
Again, this is a satisfactory check, as Eq. (82) is the conventional high-temperature result for parallel plates.

For a narrow slit we may also obtain the known result for a parallel plates configuration more generally. In the wave equation the term $`l(l+1)/r^2l(l+1)/a^2`$ is replaceable with $`k_{}^2`$ where $`𝐤_{}`$ is the transverse wave vector, i.e.,

$$\nu ^2=(l+\frac{1}{2})^2l(l+1)=k_{}^2a^2.$$
(89)
When $`l`$ is large we can regard it as continuous quantity, whereby the sum can be replaced by an integral. We have then

$$\underset{l=1}{\overset{\mathrm{}}{}}(2l+1)(2l+1)𝑑l=2a^2k_{}𝑑k_{}.$$
(90)
Further,

$$\xi nt=\frac{2\pi n}{\beta }d=Kd,$$

$$\xi \nu =\frac{d}{a}k_{}a=k_{}d,$$
(91)
or

$$2\xi \sqrt{\nu ^2+n^2t^2}=2qd,\text{with}q^2=k_{}^2+K^2.$$
(92)
Insertion of this into Eq. (76) yields

$$\beta F=4a^2\underset{n=0}{\overset{\mathrm{}}{}}^{}_{\zeta _n}^{\mathrm{}}q𝑑q\mathrm{ln}(1e^{2qd}),$$
(93)
using $`qdq=k_{}dk_{}`$. The surface force density thus becomes ($`ba`$)

$$f_b=\frac{1}{4\pi a^2}\frac{F}{d}=\frac{2}{\pi \beta }\underset{n=0}{\overset{\mathrm{}}{}}^{}_{\zeta _n}^{\mathrm{}}q^2𝑑q\frac{e^{2qd}}{(1e^{2qd})},$$
(94)
with $`\zeta _n=K=2\pi n/\beta `$ being the Matsubara frequency. This is in agreement with Eq. (2.9) in  ($`A_n=B_n=1`$ for $`\epsilon =\mathrm{}`$). It is also in agreement with Eq. (3.8) in  (it should be mentioned that $`q^2`$ in our present notation, Eq. (86), is the same as $`\kappa ^2`$ in , and also that the distance $`d`$ above is the same as $`a`$ in  and ). Note that whereas the expression (88) presupposes a narrow slit (large $`l`$), there is no restriction on the temperature.

After these preliminary analytic considerations we now present numerically calculated results for the free energy, when the walls are conducting ($`\epsilon =\mathrm{}`$). All results are given in nondimensional form. The numerics turned out to be rather demanding; as preliminary tests indicated that Matlab would be insufficient for our purpose we turned to standard FORTRAN routines and made use of them throughout. On a logarithmic plot with base 10, Fig.1 shows how $`\mathrm{lg}(\beta Ft)=\mathrm{lg}(2\pi aF)`$ varies with relative width $`d/a`$ for various values of the nondimensional temperature $`t=2\pi a/\beta `$. At zero temperature, an integration routine was used for the $`x`$ integral in Eq. (69). At finite temperatures, the double sum in Eq. (68) was calculated as it stands (thus without expansion procedures for the Riccati-Bessel functions), with use of the FORTRAN library for the Bessel functions of half-integer order. Allowing the numerical tolerances in the $`l`$ sum as well as in the $`n`$ sum to be equal to $`10^6`$, we found for the case of $`t=0.01`$ and $`d/a=0.1`$ the necessary number of terms in the $`n`$ sum to be about 415 000. For larger widths the necessary number of terms turned out to be considerably less; for instance for $`d/a=1`$ and the same $`t`$ the number was about 8900.

A characteristic property of the curves in Fig.1 is that they tend to overlap in the case of low temperatures. Thus the curve calculated for $`t=0`$ (via an $`x`$ integral and an $`l`$ sum) is indistinguishable from other curves calculated in the whole temperature region (via a double sum) up to $`t=1`$. Numerically, for $`d/a=0.1`$ the difference in $`\mathrm{lg}(\beta Ft)`$ between the cases $`t=0`$ and $`t=1`$ is found to be about $`10^4`$. For zero temperature, as mentioned, $`F`$ is the same as the energy $`E`$.

Whereas the representation in Fig.1 is most useful for low temperatures, we show in Fig.2 the representation of $`\mathrm{lg}(\beta F)`$ versus $`d/a`$. This is convenient for high temperatures, since now the curves for high $`t`$ stay inside the figure and tend to overlap. The curve calculated for $`t=50`$ is actually indistinguishable from the shown curve referring to $`t=200`$. This fact reflects that $`F`$ is proportional to $`t`$, thus in accordance with the behaviour of high temperature mutual free energies for classical harmonic oscillators in general. For a narrow slit, we expect that the calculation agrees with the approximate formula (82). We may check this in the case of $`t=200`$, $`d/a=0.05`$: the machine calculation then yields $`\beta F=249.7`$, whereas Eq. (82) yields $`\beta F=\frac{1}{2}\zeta (3)(a/d)^2=240.4`$, thus an error of 4 %. The reason why the accuray here is only moderate, is most likely that the width parameter $`d/a=0.05`$ is not small enough to represent a narrow slit to a high precision. Generally, it turned out to be difficult to calculate cases of higher temperatures or more narrow slits than those shown in the figures, without entering into special alterations of the FORTRAN routines.

Finally, it is of interest to display explicitly the free energy’s low-temperature plateau, and its high-temperature proportionality to $`t`$, for a fixed value of the relative width. This is done in Fig.3, for the cases of $`d/a=\{0.05,0.075,0.1\}`$. The horisontal plateau is seen to prevail quite accurately until a gradual increase takes place in the region roughly between $`t=10`$ and $`t=30`$ ($`\mathrm{lg}30=1.477`$). It is notworthy that this behaviour is in agreement with the following simple physical argument: The most significant frequencies $`\omega `$ contributing to $`F`$ are generally of the same order as the inverse width of the gap, ı.e. $`\omega 1/d`$. Now, from Wien’s displacement law we know that the maximum of a blackbody distribution occurs at a frequency of $`\omega _m=2.8/\beta `$. Temperature effects are expected to become significant when $`\omega `$ is comparable to $`\omega _m`$. Putting $`\omega \omega _m`$ we obtain $`t=2\pi a/\beta 2a/d`$. In the present case this amounts to $`t2040`$, ($`\mathrm{lg}t1.31.6`$), which is seen to be in good agreement with the location of the shoulder in Fig. 3. Moreover, for higher temperatures, the proportionality of $`F`$ to $`t`$ is clear from the figure.

Acknowledgement

We thank Gabriel Barton for sending us a copy of his recent preprint . The reader is referred also to the finite-temperature paper of Klich et al. .

Figure Captions

Figure 1

Logarithm (base 10) of mutual nondimensional free energy, $`\mathrm{lg}(\beta Ft)=\mathrm{lg}(2\pi aF)`$, versus relative width $`d/a`$ for various values of the nondimensional temperature $`t=2\pi a/\beta `$. For $`0t<1`$ the curves are overlapping (i.e., only one curve is drawn), consistent with Fig.3.

Figure 2

Same as Fig.1, but $`\mathrm{lg}(\beta F)`$ is shown, as appropriate for the case of high temperatures. For $`t`$ larger than about 50 the curves are overlapping (only one curve is drawn), consistent with Fig.3.

Figure 3

Variation of $`F`$ versus $`t`$ for the case of $`d/a=\{0.05,0.075,0.1\}`$.


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# Transitions induced by the discreteness of molecules in a small autocatalytic system

(February 7, 2001)

## Abstract

Autocatalytic reaction system with a small number of molecules is studied numerically by stochastic particle simulations. A novel state due to fluctuation and discreteness in molecular numbers is found, characterized as extinction of molecule species alternately in the autocatalytic reaction loop. Phase transition to this state with the change of the system size and flow is studied, while a single-molecule switch of the molecule distributions is reported. Relevance of the results to intracellular processes are briefly discussed.

PACS numbers: 87.16.-b, 05.40.-a

Cellular activities are supported by biochemical reactions in a cell. To study biochemical dynamic processes, rate equation for chemical reactions are often adopted for the change of chemical concentrations. However, the number of molecules in a cell is often rather small , and it is not trivial if the rate equation approach based on the continuum limit is always justified. For example, in cell transduction even a single molecule can switch the biochemical state of a cell . In our visual system, a single photon in retina is amplified to a macroscopic level .

Of course, fluctuations due to a finite number of molecules is discussed by stochastic differential equation (SDE) adding a noise term to the rate equation for the concentration . This noise term sometimes introduces a non-trivial effect, as discussed as noise-induced phase transition , noise-induced order , stochastic resonance , and so forth. Still, these studies assume that the average dynamics are governed by the continuum limit, and the noise term is added as a perturbation to it.

In a cell, often the number of some molecules is very small, and may go down very close to or equal to 0. In this case, the change of the number between zero and nonzero, together with the fluctuations may cause a drastic effect that cannot be treated by SDE. Possibility of some order different from macroscopic dissipative structure is also discussed by Mikhailov and Hess  (see also Ref. ). Here we present a simple example with a phenomenon intrinsic to a system with a small number of molecules where both the fluctuations and digitality(‘0/1’) are essential.

In nonlinear dynamics, drastic effect of a single molecule may be expected if a small change is amplified. Indeed, autocatalytic reaction widely seen in a cell, provides a candidate for such amplification . Here we consider the simplest example of autocatalytic reaction networks (loops) with a non-trivial finite-number effect. With a cell in mind, we consider reaction of molecules in a container, contacted with a reservoir of molecules. The autocatalytic reaction loop is $`X_i+X_{i+1}2X_{i+1};i=1,\mathrm{},k;X_{k+1}X_1`$ within a container. Through the contact with a reservoir, each molecule $`X_i`$ diffuses in and out.

Assuming that the chemicals are well stirred in the container, our system is characterized by the number of molecules $`N_i`$ of the chemical $`X_i`$ in the container with the volume $`V`$ . In the continuum limit with a large number of molecules, the evolution of concentrations $`x_iN_i/V`$ is represented by

$$dx_i/dt=r_ix_{i1}x_ir_{i+1}x_ix_{i+1}+D_i(s_ix_i)$$
(1)
where $`r_i`$ is the reaction rate, $`D_i`$ is the diffusion rate across the surface of the container, and $`s_i`$ is the concentration of the molecule in the reservoir.

For simplicity, we consider the case $`r_i=r`$, $`D_i=D`$, and $`s_i=s`$ for all $`i`$, while the phenomena to be presented here will persist by dropping this condition. With this homogeneous parameter case, the above equation has a unique attractor, a stable fixed point solution with $`x_i=s`$. The Jacobi matrix around this fixed point solution has a complex eigenvalue, and the fluctuations around the fixed point relax with the frequency $`\omega _prs/\pi `$. In the present paper we mainly discuss the case with $`k=4`$, since it is the minimal number to see the new phase to be presented.

If the number of molecules is finite but large, the reaction dynamics can be replaced by Langevin equation by adding a noise term to eq. (1). In this case, the concentration $`x_i`$ fluctuates around the fixed point, with the dynamics of a component of the frequency $`\omega _p`$. No remarkable change is observed with the increase of the noise strength, that corresponds to the decrease of the total number of molecules.

To study if there is a phenomenon that is outside of this SDE approach, we have directly simulated the above autocatalytic reaction model, by colliding molecules stochastically. Taking randomly a pair of particles and examining if they can react or not, we have made the reaction with the probability proportional to $`r`$. On the other hand, the diffusion out to the reservoir is taken account of by randomly sampling molecules and probabilistically removing them with in proportion to the diffusion rate $`D`$, while the flow to the container is also carried out stochastically in proportion to $`s`$, $`D`$ and $`V`$ . Technically, we divide time into time interval $`\delta t`$ for computation, where one pair for the reaction, and single molecules for diffusion in and out are checked. The state of the container is always updated when a reaction or a flow of a molecule has occurred. The reaction $`X_i+X_{i+1}2X_{i+1}`$ is made with the probability $`P_{Ri}(t,t+\delta t)rx_i(t)x_{i+1}(t)V\delta t=rN_i(t)N_{i+1}(t)V^1\delta t`$ within the step $`\delta t`$. A molecule diffuses out with the probability $`P_{Oi}DVx_i(t)=DN_i(t)`$, and flows in with $`P_{Ii}DVs`$. We choose $`\delta t`$ small enough so that the numerical result is insensitive with the further decrease of $`\delta t`$. By decreasing $`Vs`$, we can control the average number of molecules in the container, and discuss the effect of a finite number of molecules, since the average of the total number of molecules $`N_{tot}`$ is around the order of $`4Vs`$ . On the other hand, the ‘discreteness’ in the diffusion is clearer as the diffusion rate $`D`$ is decreased. We set $`r=1`$ and $`s=1`$, without loss of generality ($`rs/D`$ and $`sV`$ are the only relevant parameters of the model by properly scaling the time $`t`$).

First, our numerical results agree with those obtained by the corresponding Langevin equation if $`D`$ and $`V`$ are not too small. As the volume $`V`$ (and accordingly $`N_{tot}`$) is decreased, however, we have found a new state whose correspondent does not exist in the continuum limit. An example of the time series is plotted in Fig. 1, where we note a novel state with $`N_1,N_31`$ and $`N_2,N_40`$ or $`N_2,N_41`$ and $`N_1,N_30`$. To characterize this state quantitatively, we have measured the probability distribution of $`zx_1+x_3(x_2+x_4)`$. Since the solution of the continuum limit is $`x_i=s(=1)`$ for all $`i`$, this distribution has a sharp peak around 0, with a Gaussian form approximately, when $`N_{tot}`$is large enough. As shown in Fig. 2, the distribution starts to have double peaks around $`\pm 4`$, as $`V`$ is decreased. With the decrease of $`V`$ (i.e., $`N_{tot}`$), these double peaks first sharpen, and then get broader with the further decrease due to too large fluctuation of a system with a small number of molecules. Hence the new state with switches between 1-3 rich and 2-4 rich temporal domains is a characteristic phenomenon that appears only within some range of a small number of molecules .

The stability of this state is understood as follows. Consider the case with 1-3 rich and $`N_2=N_4=0`$. When one (or few) $`X_2`$ molecules flow in, $`N_2`$ increases, due to the autocatalytic reaction. Then $`X_3`$ is amplified, and since $`N_2`$ is not large, $`N_2`$ soon comes back to 0 again. In short, switch from $`(N_1,0,N_3,0)`$ to $`(N_1\mathrm{\Delta },0,N_3+\mathrm{\Delta }+1,0)`$ occurs with some $`\mathrm{\Delta }`$, but the 1-3 rich state itself is maintained. In the same manner, this state is stable against the flow of $`X_4`$. The 1-3 rich state is maintained unless either $`N_1`$ or $`N_3`$ is close or equal to 0, and both $`X_2`$ and $`X_4`$ molecules flow in within the switch time. Hence the 1-3 rich state (as well as 2-4 rich state, of course) is stable as long as the flow rate is small enough.

Within a temporal domain of 1-3 rich state, switches occur to change from $`(N_1,N_3)(N_1^{},N_3^{})`$. In Fig. 3, we have plotted the probability density for the switch from $`N_1N_1^{}`$ when a single $`X_2`$ molecule flows in, amplified, and $`N_2`$ comes back to 0, by fixing $`N_1+N_3=N_{ini}`$ at 256 initially. (We assume no more flow. Hence $`N_1^{}+N_3^{}=N_{ini}+1`$). The peak around $`N_1^{}N_1+1`$ means the reaction from $`N_2`$ to $`N_3`$ before the amplification, while another peak around $`N_1^{}N_3=N_{ini}N_1`$ shows the conversion of the numbers through the amplification of $`X_2`$ molecules. Indeed, each temporal domain of the 1-3 rich state consists of successive switches of $`(N_1,N_3)(N_3,N_1)`$, as shown in Fig. 1. Since molecules diffuse out or in randomly besides this switch, the difference between $`N_1`$ and $`N_3`$ is tended to decrease. On the other hand, each 1-3 rich state, when formed, has imbalance between $`N_1`$ and $`N_3`$, i.e., $`N_1N_3`$ or $`N_1N_3`$, since, as in Fig. 1, the state is attracted from alternate amplification of $`X_i`$, where only one type $`i`$ of molecules has $`N_i1`$ and 0 for others. However, the destruction of the 1-3 rich state is easier if $`N_1N_3`$ or $`N_1N_3`$, as mentioned. Roughly speaking, each 1-3 rich state starts with a large imbalance between $`N_1`$ and $`N_3`$, and continues over a long time span, if the switch and diffusion lead to $`N_1N_3`$, and is destroyed when the large imbalance is restored. Indeed, we have plotted the distribution of $`yx_1x_3+x_2x_4`$, to see the imbalance for each 1-3 rich or 2-4 rich domain. This distribution shows double peaks clearly around $`y\pm 2.8,i.e.,(N_1,N_3)(3.4V,0.6V),(0.6V,3.4V)`$.

Let us now discuss the condition to have the 1-3 or 2-4 rich state. First, the total number of molecules should be small enough so that the fluctuation from the state $`N_iN_j`$ (for $`i,j`$) may reach the state with $`N_i0`$. On the other hand, if the total number is too small, even $`N_1`$ or $`N_3`$ for the 1-3 rich state may approach 0 easily, and the state is easily destabilized. Hence the alternately rich state is stabilized only within some range of $`V`$.

Note also that our system has conserved quantities $`_iN_i`$ (and $`_ilogx_i`$ in the continuum limit), if $`D`$ is set at $`0`$. Hence, as the diffusion rate gets smaller, some characteristics of the initial population are maintained over long time. Once the above 1-3 (or 2-4) rich state is formed, it is more difficult to be destabilized if $`D`$ is small. In Fig. 4, we have plotted the rate of the residence at 1-3 (or 2-4) rich state over the whole temporal domain, with the change of $`V`$. Roughly speaking, the state appears for $`DV<1`$ , while for too small $`V`$ (e.g., $`V<4`$), it is again destabilized by fluctuations. Although the range of the 1-3 rich state is larger for small $`D`$, the necessary time to approach it increases linearly with $`V`$. Hence it would be fair to state that properly small number of molecules is necessary to have the present state.

To sum up, we have discovered a novel state in reaction dynamics intrinsic to a small number of molecules. This state is characterized by alternately vanishing chemicals within an autocatalytic loop, and switches by a flow of single molecules . Hence, this state generally appears for a system with an autocatalytic loop consisting of any even number of elements. With the increase of $`k`$, however, the globally alternating state all over the loop is more difficult to be reached. In this case, locally alternating states are often formed with the decrease of the system size (e.g., ‘2-4-6-8 rich’ and ‘11-13-15 rich’ states for $`k=16`$). This local order is more vulnerable to the flow of molecules than the global order for the $`k=4`$ loop.

On the other hand, for $`k=3`$, two of the chemical species start to vanish for small $`V`$, since any pair of different chemical species can react so that one chemical species is quickly absorbed into the other. This state of single chemical species, however, is not stable by a flow of a single molecule. Indeed, no clear ‘phase transition’ is observed with the decrease of $`V`$.

Although in the present Letter we have studied the case with $`s_i=s`$, we have also confirmed that the present state with alternately vanishing chemical species is generally stabilized for small $`V`$, even if $`s_i`$ or $`r_i`$ or $`D_i`$ are not identical.

Last, we make a remark about the signal transduction in a cell. In a cell, often the number of molecules is small, and the cellular states often switch by a stimulus of a single molecule . Furthermore, signal transduction pathways generally include autocatalytic reactions. In this sense, the present stabilization of the alternately rich state as well as a single-molecule switch may be relevant to cellular dynamics. Of course, one may wonder that the present mechanism is too ‘stochastic’. Then, use of both the present mechanism and robustness by dynamical systems  may be important. Indeed, we have made some preliminary simulations of complex reaction networks. Often, we have found the transition to a new state at a small number of molecules, when the network includes the autocatalytic loop of 4 chemicals as studied here . Hence the state presented here is not restricted to this specific reaction network, but is observed in a class of autocatalytic reaction network. Furthermore switches between different dynamic states (limit cycles or chaos) are possible when the number of some molecules (that are not directly responsible to the switch) is large enough. The ‘switch of dynamical systems’ by the present few-number-molecule mechanism will be an important topic to be pursued in future.

We would like to thank C. Furusawa, T. Shibata and T. Yomo for stimulating discussions. This research was supported by Grants-in-Aid for Scientific Research from the Ministry of Education, Science, and Culture of Japan (Komaba Complex Systems Life Science Project).


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# Comparison of experimental data and theoretical calculations for electrical resistivity and Hall coefficient in (TMTSF)₂PF₆

## Abstract

The temperature dependences of the Hall coefficient and electrical resistivity recently measured by Moser et al. \[Phys. Rev. Lett. 84, 2674 (2000)\] in the quasi-one-dimensional organic conductor $`(\mathrm{TMTSF})_2\mathrm{PF}_6`$ are quantitatively compared with our previous theoretical calculations \[Synth. Met. 103, 2202 (1999); Eur. Phys. J. B 11, 385 (1999)\]. We find a good agreement, albeit not with a fully consistent set of parameters for the two quantities.

thanks: Corresponding author. Phone: +1-301-405-6151, Fax: +1-301-314-9465, E-mail: yakovenk@physics.umd.edu, Web: http://www2.physics.umd.edu/~yakovenk/

Recently, the temperature dependences of the Hall coefficient, as well as electrical resistivity, were measured in the quasi-one-dimensional (Q1D) organic conductor $`(\mathrm{TMTSF})_2\mathrm{PF}_6`$ by the two groups . The results were interpreted using the Luttinger liquid concept in Ref.  and the conventional Fermi liquid theory in Ref. . Before the experimental data became known, we had published theoretical calculations of the temperature dependences of the Hall coefficient  and electrical resistivity . In the present paper, we quantitatively compare our theoretical predictions and the experimental results. Since we have calculated the Hall coefficient in the (a-b) plane, we compare only with the results of Ref. , where the Hall coefficient was measured in that geometry, unlike in Ref. , were the (b-c) plane geometry was employed. Electrical resistivity, calculated in Ref.  for the direction along the chains, is compared only with the experimental results of Ref. , because they correspond to constant volume, unlike the constant-pressure results of Ref. .

The Hall coefficient $`R_H=\sigma _{xy}/H\sigma _{xx}\sigma _{yy}`$, where $`\sigma _{ij}`$ are the components of the conductivity tensor and $`H`$ is the magnetic field, is usually a constant, because, in a simple Drude model, $`\sigma _{xy}\tau ^2`$ and $`\sigma _{xx,yy}\tau `$, so the temperature-dependent relaxation time $`\tau `$ cancels out in $`R_H`$. However, the experiment  found that $`R_H`$ in $`(\mathrm{TMTSF})_2\mathrm{PF}_6`$ does depend on temperature. The authors invoked the Luttinger liquid concept in order to explain this effect. However, it has been shown theoretically that $`R_H`$ of weakly coupled one-dimensional Luttinger chains does not depend on frequency and temperature , because the power-law dependences of $`\sigma _{xy}`$ and $`\sigma _{yy}`$ cancel out.

The Hall coefficient may depend on temperature if the system has relaxation times with different temperature dependences. (See discussion  of the “cold spots” for the cuprate high-temperature superconductors, where $`R_H`$ is also temperature-dependent.) In Ref. , we had calculated the distribution of the umklapp scattering rates over the Fermi surface of a Q1D conductor and found that at low temperatures “hot spots” develop with a different temperature dependence. Using this distribution, we have calculated the temperature dependence of $`R_H`$ in Ref. . Fig. 1 shows our theoretical curve with the experimental points from Ref. . In our calculation, the Hall coefficient consists of two terms: $`R_H=R_H^{(0)}+R_H^{(1)}`$. The first term is a temperature-independent band-structure contribution. In our fit, it is taken to be $`R_H^{(0)}=6.1\times 10^9\mathrm{m}^3/\mathrm{C}`$, which is 1.7 times greater than the value assumed in Ref. . The second, temperature-dependent term $`R_H^{(1)}`$ is obtained by multiplying curve (a) of Fig. 1 from Ref.  by the factor $`\alpha _R=2.3\times 10^7\mathrm{m}^3/\mathrm{C}`$. That corresponds to $`p_Fv_F/t_b=38`$, which is 0.57 of the value assumed in Ref. . The temperature scale of Fig. 1 from Ref.  is increased by the factor $`\alpha _T=2.7`$, which means that the transverse tunneling amplitudes $`t_b`$ and $`t_b^{}`$ are taken to be $`\alpha _T`$ times greater than the values 300 K and 30 K assumed in Ref. . Line (a) in Fig. 1 of Ref.  corresponds to the phases $`\phi =\phi ^{}=0`$ in the transverse electron dispersion law (see the definitions in Ref. ). The other curves shown in Fig. 1 of Ref.  for different values of the phases qualitatively disagree with the experimental behavior .

In Ref.  we have calculated the temperature dependence of electrical resistivity $`R_{xx}`$ along the chains by taking into account renormalization of umklapp scattering. Fig. 2 shows our theoretical curve with the experimental points from Ref. . The theoretical line is taken from Fig. 4 of Ref.  with the parameters $`\phi =\pi /4`$, $`\phi ^{}=2\phi `$, $`t_b=290`$ K, $`t_b^{}=`$ 20 K, and the temperature scale is increased by the factor $`\alpha _T=1.3`$. The vertical scale of Fig. 4 of Ref.  is multiplied by the factor $`\alpha _R=0.23`$.

Overall, the theory correctly captures the experimental features. However, the sets of model parameters utilized to obtain the fits in Figs. 1 and 2 are not the same. First, the values of the phases $`\phi `$ and $`\phi ^{}`$ are different. The Hall coefficient is very sensitive to the choice of $`\phi `$ and $`\phi ^{}`$, and a sensible fit is possible only when the phases are zero or close to zero. On the other hand, $`R_{xx}`$ is less sensitive to the choice of the phases. If the phases are zero, the main problem is the upturn of $`R_{xx}`$ when temperature approaches to the SDW transition temperature (see Fig. 4 of Ref. ). The upturn can be suppressed by selecting a small but finite value for the phases (see the other curves in Fig. 4 of Ref. ) or by selecting a greater value for $`t_b^{}`$ (see Fig. 6 of Ref. ). The second problem is the difference in the temperature scales $`\alpha _T`$ utilized to obtain the fits in Figs. 1 and 2. While the scale 1.3 for $`R_{xx}`$ is reasonable, the value 2.7 for $`R_H`$ is too big. However, the scale of $`R_H`$ is controlled primarily by $`t_b^{}`$ (because $`R_H^{(1)}=0`$ if $`t_b^{}=0`$ ), whereas the scale of $`R_{xx}`$ is controlled by $`t_b`$. So the agreement could be achieved by increasing $`t_b^{}`$ without increasing $`t_b`$. The increase of $`t_b^{}`$ could suppress the SDW transition, which is present at the ambient pressure, but that could be compensated by an increase in the interaction strength.

The space of model parameters is big, and there are opportunities to achieve better agreement with the experiment by optimizing the choice of parameters. Our first try presented here appears to be promising.


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# Low-Energy Effective Action in N=4 Super Yang-Mills Theories

## 1 Introduction

Low-energy structure of quantum supersymmetric field theories is described by the effective lagrangians of two types: chiral and general or holomorphic and non-holomorphic. Non-holomorphic or general contributions to effective action are given by integrals over full superspace while holomorphic or chiral contributions are given by integrals over chiral subspace of superspace. As a result the effective action in low-energy limit is defined by the chiral superfield $``$ which is called holomorphic or chiral effective potential and real superfield $``$ which is called non-holomorphic or general effective potential. The specific feature of these potentials is that they do not depend on covariant derivatives of the superfields.

We point out that a possibility of holomorphic corrections to effective action was firstly demonstrated in  ( see also ) for N=1 SUSY and in  for N=2 SUSY. The modern interest to structure of low-energy effective action in extended supersymmetric theories was inspired by the seminal papers  where exact instanton contribution to holomorphic effective potential has been found for N=2 SU(2) super Yang-Mills theory. These results have later been extended for various gauge groups and for coupling to matter (see f.e. ). One can show that in generic N=2 SUSY models namely the holomorphic effective potential is leading low-energy contribution. Non-holomorphic potential is next to leading correction. A detailed investigation of structure of low-energy effective action for various N=2 SUSY theories has been undertaken in \[6-9\].

A further study of quantum aspects of supersymmetric field models leads to problem of effective action in N=4 SUSY theories. These theories being maximally extended global supersymmetric models possess the remarkable properties on quantum level:

* N=4 super Yang-Mills model is finite quantum field theory,
* N=4 super Yang-Mills model is superconformal invariant theory and hence, its effective action can not depend on any scale. These properties allow to analyze a general form of low-energy effective action and see that it changes drastically in compare with generic N=2 super Yang-Mills theories.

Analysis of structure of low-energy effective action in N=4 SU(2) SYM model spontaneously broken down to U(1) has been fulfilled in recent paper by Dine and Seiberg . They have investigated a part of effective action depending on N=2 superfield strengths $`W`$, $`\overline{W}`$ and shown

* Holomorphic quantum corrections are trivial in N=4 SYM. Therefore, namely non-holomorphic effective potential is leading low-energy contribution to effective action,
* Non-holomorphic effective potential $`(W,\overline{W})`$ can be found on the base of the properties of quantum N=4 SYM theory up to a coefficient. All perturbative or non-perturbative corrections do not influence on functional form of $`(W,\overline{W})`$ and concern only this coefficient.

The approaches to direct calculation of non-holomorphic effective potential including the above coefficient have been developed in \[11-13\], extensions for gauge group SU(n) spontaneously broken to maximal torus have been given in \[15-17\] (see also  where some bosonic contributions to low-energy effective action have been found).

## 2 N=4 super Yang-Mills theory in harmonic superspace

As well known, the most powerful and adequate approach to investigate the quantum aspects of supersymmetric field theories is formulation of these theories in terms of unconstrained superfields carrying out a representation of the supersymmetry. Unfortunately such a manifestly N=4 supersymmetric formulation for N=4 Yang-Mills theory is still unknown. A purpose of this paper is study a structure of low-energy effective action for N=4 SYM as a functional of N=2 superfield strengths. In this case it is sufficient to realize the N=4 SYM theory as a theory of N=2 unconstrained superfields. It is naturally achieved within harmonic superspace. The N=2 harmonic superspace  is the only manifestly N=2 supersymmetric formalism allowing to describe general N=2 supersymmetric field theories in terms of unconstrained N=2 superfields. This approach has been successfully applied to problem of effective action in various N=2 models in recent works .

From point of view of N=2 SUSY, the N=4 Yang-Mills theory describes interaction of N=2 vector multiplet with hypermultiplet in adjoint representation. Within harmonic superspace approach, the vector multiplet is realized by unconstrained analytic gauge superfield $`V^{++}`$. As to hypermultiplet, it can be described either by a real unconstrained superfield $`\omega `$ ($`\omega `$-hypermultiplet) or by a complex unconstrained analytic superfield $`q^+`$ and its conjugate ($`q`$-hypermultiplet). In the $`\omega `$-hypermultiplet realization, the classical action of N=4 SYM model has the form

$$S[V^{++},\omega ]=\frac{1}{2g^2}\mathrm{tr}d^4xd^4\theta W^2\frac{1}{2g^2}\mathrm{tr}𝑑\zeta ^{(4)}^{++}\omega ^{++}\omega $$
$`(1)`$
The first terms here is pure N=2 SYM action and the second term is action $`\omega `$-hypermultiplet. In $`q`$-hypermultiplet realization, the action of the N=4 SYM model looks like this

$$S[V^{++},q^+,\stackrel{+}{\stackrel{}{q}}]=\frac{1}{2g^2}\mathrm{tr}d^4xd^4\theta W^2\frac{1}{2g^2}\mathrm{tr}𝑑\zeta ^{(4)}q^{+i}^{++}q_i^+$$
$`(2)`$
where

$$q_i^+=(q^+,\stackrel{+}{\stackrel{}{q}}),q^{i+}=\epsilon ^{ij}q_j^+=(\stackrel{+}{\stackrel{}{q}},q^+)$$
$`(3)`$
All other denotions are given in . Both models (1,2) are classically equivalent and manifestly N=2 supersymmetric by construction. However, as has been shown in , both these models possess hidden N=2 supersymmetry and as a result they actually are N=4 supersymmetric.

## 3 General form of non-holomorphic effective potential

We study the effective action $`\mathrm{\Gamma }`$ for N=4 SYM with gauge group SU(2) spontaneously broken down to U(1). This effective action is considered as a functional of N=2 superfield strengths $`W`$ and $`\overline{W}`$. Then holomorphic effective potential $``$ depends on chiral superfield $`W`$ and it is integrated over chiral subspace of N=2 superspace with the measure $`d^4xd^4\theta `$. Non-holomorphic effective potential $``$ depends on both $`W`$ and $`\overline{W}`$. It is integrated over full N=2 superspace with the measure $`d^4xd^8\theta `$. Let us begin with dimensional analysis of low-energy effective action. Taking into account the mass dimensions of $`W`$, $`(W)`$, $`(W,\overline{W})`$ and the superspace measures $`d^4xd^4\theta `$ and $`d^4xd^8\theta `$ ones write

$$(W)=W^2f\left(\frac{W}{\mathrm{\Lambda }}\right),(W,\overline{W})=(\frac{W}{\mathrm{\Lambda }},\frac{\overline{W}}{\mathrm{\Lambda }})$$
$`(4)`$
where $`\mathrm{\Lambda }`$ is some scale and $`f(\frac{W}{\mathrm{\Lambda }})`$ and $`(\frac{W}{\mathrm{\Lambda }},\frac{\overline{W}}{\mathrm{\Lambda }})`$ are the dimensionless functions of their arguments. Due to remarkable properties of N=4 SYM in quantum domain, the effective action is scale independent. Therefore

$$\mathrm{\Lambda }\frac{d}{d\mathrm{\Lambda }}d^4xd^4\theta W^2f\left(\frac{W}{\mathrm{\Lambda }}\right)=0,\mathrm{\Lambda }\frac{d}{d\mathrm{\Lambda }}d^4xd^8\theta (\frac{W}{\mathrm{\Lambda }},\frac{\overline{W}}{\mathrm{\Lambda }})=0$$
$`(5)`$
First of eqs (5) leads to $`f(\frac{W}{\mathrm{\Lambda }})=const`$. Second of eqs (5) reads

$$\mathrm{\Lambda }\frac{d}{d\mathrm{\Lambda }}=g\left(\frac{W}{\mathrm{\Lambda }}\right)+\overline{g}\left(\frac{\overline{W}}{\mathrm{\Lambda }}\right)$$
$`(6)`$
Here $`g`$ is arbitrary chiral function of chiral superfield $`\frac{W}{\mathrm{\Lambda }}`$ and $`\overline{g}`$ is conjugate function. The integrals of $`g`$ and $`\overline{g}`$ over full N=2 superspace vanish and eqs(5) takes place for any $`g`$ and $`\overline{g}`$. Since $`f(\frac{W}{\mathrm{\Lambda }})=const`$ the holomorphic effective potential $`(W)`$ is proportional to classical lagrangian $`W^2`$. General solution to eq (6) is written as follows

$$(\frac{W}{\mathrm{\Lambda }},\frac{\overline{W}}{\mathrm{\Lambda }})=c\mathrm{log}\frac{W^2}{\mathrm{\Lambda }^2}\mathrm{log}\frac{\overline{W}^2}{\mathrm{\Lambda }^2}$$
$`(7)`$
with arbitrary coefficient $`c`$. As a result, holomorphic effective potential is trivial in N=4 SYM theory. Therefore, namely non-holomorphic effective potential is leading low-energy quantum contribution to effective action. Moreover, the non-holomorphic effective potential is found exactly up to coefficient and given by eq (7) . Any perturbative or non-perturbative quantum corrections are included into a single constant $`c`$. However, this result immediately face the problems:

* is there exist a calculational procedure allowing to derive $`(W/\mathrm{\Lambda },\overline{W}/\mathrm{\Lambda })`$ in form (7) within a model?
* what is value of $`c`$? If $`c=0`$, the non-holomorphic effective potential vanishes and low-energy effective action in N=4 SYM is defined by the terms in effective action depending on the covariant derivatives of $`W`$ and $`\overline{W}`$,
* what is structure of non-holomorphic effective potential for the other then SU(2) gauge groups?

The answers all these questions have been given in \[11-17\]. Further we are going to discuss a general manifestly N=2 supersymmetric and gauge invariant procedure of deriving the non-holomorphic effective potential in one-loop approximation . This procedure is based on the following points:

* formulation of N=4 SYM theory in terms of N=2 unconstrained superfields in harmonic superspace ,
* N=2 background field method  providing manifest gauge invariance on all steps of calculations,
* Identical transformation of path integral for effective action over N=2 superfields to path integral over some N=1 superfields. This point is nothing more then replacement of variables in path integral,
* Superfield proper-time technique (see first of refs ) which is manifestly covariant method for evaluating effective action in superfield theories.

Next section is devoted to some details of calculating non-holomorphic effective potential.

## 4 Calculation of non-holomorphic effective potential

We study effective action for the classically equivalent theories (1, 2) within N=2 background field method . We assume also that the gauge group of these theories is SU(n). In accordance with background field method , the one-loop effective action in both realizations of N=4 SYM is given by

$$\mathrm{\Gamma }^{(1)}[V^{++}]=\frac{i}{2}\mathrm{Tr}_{(2,2)}\mathrm{log}\stackrel{}{\mathrm{}}\frac{i}{2}\mathrm{Tr}_{(4,0)}\mathrm{log}\stackrel{}{\mathrm{}}$$
$`(8)`$
where $`\stackrel{}{\mathrm{}}`$ is the analytic d’Alambertian introduced in .

$$\begin{array}{ccc}\hfill \stackrel{}{\mathrm{}}& =& 𝒟^m𝒟_m+\frac{i}{2}(𝒟^{+\alpha }W)𝒟_\alpha ^{}+\frac{i}{2}(\overline{𝒟}_{\dot{\alpha }}^+\overline{W})\overline{𝒟}^{\dot{\alpha }}\hfill \\ & & \frac{i}{4}(𝒟^{+\alpha }𝒟_\alpha ^+W)𝒟^{}+\frac{i}{8}[𝒟^{+\alpha },𝒟_\alpha ^{}]W+\frac{i}{2}\{\overline{W},W\}\hfill \end{array}$$
$`(9)`$
The formal definitions of the $`\mathrm{Tr}_{(2,2)}\mathrm{log}\stackrel{}{\mathrm{}}`$ and $`\mathrm{Tr}_{(4,0)}\mathrm{log}\stackrel{}{\mathrm{}}`$ are given in . Our purpose is finding of non-holomorphic effective potential $`(W,\overline{W})`$ where the constant superfields $`W`$ and $`\overline{W}`$ belong to Cartan subalgebra of the gauge group SU(n). Therefore, for calculation of $`(W,\overline{W})`$ it is sufficient to consider on-shell background

$$𝒟^{\alpha (i}𝒟_\alpha ^{j)}W=0$$
$`(10)`$
In this case the one-loop effective action (8) can be written in the form

$$\mathrm{exp}(i\mathrm{\Gamma }^{(1)})=\frac{𝒟^{++}\mathrm{exp}\left\{\frac{i}{2}\mathrm{tr}𝑑\zeta ^{(4)}^{++}\stackrel{}{\mathrm{}}^{(++)}\right\}}{𝒟^{++}\mathrm{exp}\left\{\frac{i}{2}\mathrm{tr}𝑑\zeta ^{(4)}^{++}^{++}\right\}}$$
$`(11)`$
The superfield $`^{++}`$ belonging to the adjoint representation looks like $`^{++}=^{ij}u_i^+u_j^+`$ with $`u_i^+`$ be the harmonics  and $`^{ij}=^{ji}`$ satisfy the constraints

$$𝒟_\alpha ^{(i}^{jk)}=\overline{𝒟}_{\dot{\alpha }}^{(i}^{jk)}=0,\overline{}^{ij}=_{ij}$$
$`(12)`$
The next step is transformation of the path integral (11) to one over unconstrained N=1 superfields. This point is treated as replacement of variables in path integral (11). We introduce the N=1 projections of $`W`$ ( see the details in ). As a result one obtains

$$\mathrm{\Gamma }^{(1)}=\underset{k<l}{}\mathrm{\Gamma }_{kl},\mathrm{\Gamma }_{kl}=i\mathrm{Tr}\mathrm{log}\mathrm{\Delta }_{kl}$$
$`(13)`$
where

$$\mathrm{\Delta }_{kl}=𝒟^m𝒟_m(W^{k\alpha }W^{l\alpha })𝒟_\alpha +(\overline{W}_{\dot{\alpha }}^k\overline{W}_{\dot{\alpha }}^l)\overline{𝒟}^{\dot{\alpha }}+|\mathrm{\Phi }^k\mathrm{\Phi }^l|^2$$
$`(14)`$
and $`𝒟_m`$, $`𝒟_\alpha `$, $`\overline{𝒟}_{\dot{\alpha }}`$ are the supercovariant derivatives. Here

$$\mathrm{\Phi }=\mathrm{diag}(\mathrm{\Phi }^1,\mathrm{\Phi }^2,\mathrm{},\mathrm{\Phi }^n),\underset{k=1}{\overset{n}{}}\mathrm{\Phi }^k=0.$$
$`(15)`$
$$W_\alpha =\mathrm{diag}(W_\alpha ^1,\mathrm{},W_\alpha ^n),\underset{k=1}{\overset{n}{}}W_\alpha ^k=0$$

The operator (14) has been introduced in . Thus, we get a problem of effective action associated with N=1 operator (14). Such a problem can be investigated within N=1 superfield proper-time technique. Application of this technique leads to lowest contribution to effective action in the form

$$\mathrm{\Gamma }_{kl}=\frac{1}{(4\pi )^2}d^8z\frac{W^{\alpha kl}W_\alpha ^{kl}\overline{W}_{\dot{\alpha }}^{kl}\overline{W}^{\dot{\alpha }kl}}{(\mathrm{\Phi }^{kl})^2(\overline{\mathrm{\Phi }}^{kl})^2}$$
$`(16)`$
where

$$\mathrm{\Phi }^{kl}=\mathrm{\Phi }^k\mathrm{\Phi }^l,W^{kl}=W^kW^l$$
$`(17)`$
Eqs (13, 16, 17) define the non-holomorphic effective potential of N=4 SYM theory in terms of N=1 projections of N=2 superfield strengths. The last step is restoration of N=2 form of effective action (16). For this purpose we write contribution of non-holomorphic effective potential to effective action in terms of covariantly constant N=1 projections $`\mathrm{\Phi }`$ and $`W_\alpha `$

$$d^4xd^8\theta (W,\overline{W})=d^8zW^\alpha W_\alpha \overline{W}_{\dot{\alpha }}\overline{W}^{\dot{\alpha }}\frac{^4(\overline{\mathrm{\Phi }},\mathrm{\Phi })}{\mathrm{\Phi }^2\overline{\mathrm{\Phi }}^2}+\mathrm{derivatives}$$
$`(18)`$
Comparison of eqs (17) and (18) leads to

$$\mathrm{\Gamma }^{(1)}=d^4xd^8\theta (\overline{W},W)$$

$$(W,\overline{W})=\frac{1}{(8\pi )^2}\underset{k<l}{}\mathrm{log}\left(\frac{(\overline{W}^k\overline{W}^l)^2}{\mathrm{\Lambda }^2}\right)\mathrm{log}\left(\frac{(W^kW^l)^2}{\mathrm{\Lambda }^2}\right)$$
$`(19)`$
Eq (19) is our final result. In partial case of SU(2) group spontaneously broken down to U(1) eq (19) coincides with eq (7) where $`c=1/(8\pi ^2)`$.

## 5 Discussion

Eq (19) defines the non-holomorphic effective potential depending on N=2 superfield strengths for N=4 SU(n) super Yang-Mills theories. As a result we answered all the questions formulated in section 3. First, we have presented the calculational procedure allowing to find non-holomorphic effective potential. Second, we calculated the coefficient c in eq (7) for SU(2) group. It is equal to $`1/(8\pi )^2`$. Third, a structure of non-holomorphic effective potential for the gauge group SU(n) has been established. It is interesting to point out that the scale $`\mathrm{\Lambda }`$ is absent when the non-holomorphic effective potential (19) is written in terms of N=1 projections of $`W`$ and $`\overline{W}`$ (see eqs (15, 16)). Therefore, the $`\mathrm{\Lambda }`$ will be also absent if we write the non-holomorphic effective potential through the components fields. We need in $`\mathrm{\Lambda }`$ only to present the final result in manifestly N=2 supersymmetric form. N=1 form of non-holomorphic effective potential (16) allows very easy to get leading bosonic component contribution. Schematically it has the form $`F^4/|\varphi |^4`$, where $`F_{mn}`$ is abelian strength constructed from vector component and $`\varphi `$ is a scalar component of N=2 vector multiplet. It means that non-zero expectation value of scalar field $`\varphi `$ plays a role of effective infrared regulator in N=4 SYM theories. Generalization of low-energy effective action considered in \[10-17\] and containing all powers of constant $`F_{mn}`$ has recently been constructed in  in terms of N=2 superconformal invariants. The direct proof of absence of three- and four-loop corrections to $``$ was given in .

Acknowledgments. I am very grateful to E.I. Buchbinder, E.I. Ivanov, S.M. Kuzenko, B.A. Ovrut, A.Yu Petrov, A.A. Tseytlin for collaboration and valuable discussions. The work was supported in part by the RFBR grant 99-02-16617, RFBR-DFG grant 99-02-04022, INTAS grant 991-590, GRACENAS grant 97-6.2-34, NATO collaborative research grant PST.CLG 974965 and FAPESP grant. I thank Institute of Physics, University of Sao Paulo for hospitality.