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# Alignment-to-orientation conversion and nuclear quadrupole resonance

## Appendix A Theory

The Hamiltonian governing the NQR dynamics in the presence of an rf field is derived, for example, in Ref. Lee2002 . It is convenient to represent this Hamiltonian in the $`(|x,|y,|z)`$ Cartesian basis777Defined by $`|x=\left(|M=1|M=+1\right)/\sqrt{2}`$, $`|y=i\left(|M=1+|M=+1\right)/\sqrt{2}`$, $`|z=|M=0`$. of the EFG principal axis system (oriented at Euler angles $`\alpha `$ and $`\beta `$ to the rf field), because the nuclear quadrupolar Hamiltonian (3) is diagonal in this basis. Transforming to the quadrupolar interaction frame removes the diagonal nuclear quadrupolar Hamiltonian and adds additional time-dependent terms in the off-diagonal elements. This form of the Hamiltonian, given by

$$\stackrel{~}{H}(t)=\mathrm{}\omega _1\mathrm{cos}\left(\omega t+\varphi \right)\left(\begin{array}{ccc}0& \mathrm{cos}\beta e^{\frac{2i\eta }{3}\omega _Qt}& \mathrm{cos}\alpha \mathrm{sin}\beta e^{i\left(1+\frac{\eta }{3}\right)\omega _Qt}\\ \mathrm{cos}\beta e^{\frac{2i\eta }{3}\omega _Qt}& 0& i\mathrm{sin}\alpha \mathrm{sin}\beta e^{i\left(1\frac{\eta }{3}\right)\omega _Qt}\\ \mathrm{cos}\alpha \mathrm{sin}\beta e^{i\left(1+\frac{\eta }{3}\right)\omega _Qt}& i\mathrm{sin}\alpha \mathrm{sin}\beta e^{i\left(1\frac{\eta }{3}\right)\omega _Qt}& 0\end{array}\right),$$
(6)
facilitates a low-power time-average approximation that removes rapidly oscillating terms. Assuming that the electric field gradients are cylindrically symmetric ($`\eta =0`$) and that the rf field is resonant with the quadrupolar frequency ($`\omega =\omega _Q`$), upon averaging over time-dependent terms the Hamiltonian becomes

$$\overline{H}(t)=\frac{\mathrm{}\omega _1}{2}\left(\begin{array}{ccc}0& 0& \mathrm{cos}\alpha \mathrm{sin}\beta e^{i\varphi }\\ 0& 0& i\mathrm{sin}\alpha \mathrm{sin}\beta e^{i\varphi }\\ \mathrm{cos}\alpha \mathrm{sin}\beta e^{i\varphi }& i\mathrm{sin}\alpha \mathrm{sin}\beta e^{i\varphi }& 0\end{array}\right).$$
(7)
We assume that the initial density matrix (also written in the Cartesian basis) is fully aligned along the EFG axis:

$$\rho (0)=\left(\begin{array}{ccc}0& 0& 0\\ 0& 0& 0\\ 0& 0& 1\end{array}\right).$$
(8)
The interaction-frame time dependence is given by

$$\begin{array}{cc}\hfill \stackrel{~}{\rho }(t)& =e^{i\overline{H}t/\mathrm{}}\rho (0)e^{i\overline{H}t/\mathrm{}}\hfill \\ & =\left(\begin{array}{ccc}\mathrm{cos}^2\alpha \mathrm{sin}^2\left(\frac{1}{2}\omega _1^{}t\right)& i\mathrm{cos}\alpha \mathrm{sin}\alpha \mathrm{sin}^2\left(\frac{1}{2}\omega _1^{}t\right)& \frac{i}{2}\mathrm{cos}\alpha \mathrm{sin}\left(\omega _1^{}t\right)e^{i\varphi }\\ i\mathrm{cos}\alpha \mathrm{sin}\alpha \mathrm{sin}^2\left(\frac{1}{2}\omega _1^{}t\right)& \mathrm{sin}^2\alpha \mathrm{sin}^2\left(\frac{1}{2}\omega _1^{}t\right)& \frac{1}{2}\mathrm{sin}\alpha \mathrm{sin}\left(\omega _1^{}t\right)e^{i\varphi }\\ \frac{i}{2}\mathrm{cos}\alpha \mathrm{sin}\left(\omega _1^{}t\right)e^{i\varphi }& \frac{1}{2}\mathrm{sin}\alpha \mathrm{sin}\left(\omega _1^{}t\right)e^{i\varphi }& \mathrm{cos}^2\left(\frac{1}{2}\omega _1^{}t\right)\end{array}\right),\hfill \end{array}$$
(9)
where $`\omega _1^{}=\omega _1\mathrm{sin}\beta `$. In order to find the dynamics of the powder average, we transform out of the interaction frame and rotate the coordinate system to coincide with the lab frame, with $`\stackrel{}{B}_1`$ along the quantization axis. The algebraic form of the resulting density matrix is complicated. However, since in the powder the only preferred direction is along $`\stackrel{}{B}_1`$, the powder average will be symmetric about this axis. Thus, if we represent the density matrix in the $`(|1,|0,|1)`$ Zeeman basis, the averaged density matrix will be diagonal, and we can ignore the off-diagonal terms:

$$\rho _{\mathrm{Lab}}(t)=\frac{1}{8}\left(\begin{array}{c}3\mathrm{cos}\omega _1^{}t\left(1+\mathrm{cos}\omega _1^{}t\right)\mathrm{cos}2\beta +4\mathrm{sin}\omega _1^{}t\mathrm{sin}\beta \mathrm{sin}\left(\omega t+\varphi \right)\mathrm{}\mathrm{}\\ \mathrm{}8\mathrm{cos}^2\left(\frac{1}{2}\omega _1^{}t\right)\mathrm{cos}^2\beta \mathrm{}\\ \mathrm{}\mathrm{}3\mathrm{cos}\omega _1^{}t\left(1+\mathrm{cos}\omega _1^{}t\right)\mathrm{cos}2\beta 4\mathrm{sin}\omega _1^{}t\mathrm{sin}\beta \mathrm{sin}\left(\omega t+\varphi \right)\end{array}\right).$$
(10)
To obtain the result for the powder as a whole, we average over the Euler angles, evaluating the integrals using *Mathematica* software:

$$\begin{array}{cc}\hfill \rho _{\text{avg}}(t)& =\frac{_0^{2\pi }𝑑\alpha _0^\pi \rho _{\mathrm{Lab}}(t)\mathrm{sin}\beta d\beta }{_0^{2\pi }𝑑\alpha _0^\pi \mathrm{sin}\beta d\beta }\hfill \\ & =\frac{1}{24}\left(\begin{array}{c}10+4F^{}\left(\frac{1}{4}\omega _1^2t^2\right)3\pi 𝐇_1\left(\omega _1t\right)+8F^{\prime \prime }\left(\frac{1}{4}\omega _1^2t^2\right)\omega _1t\mathrm{sin}\left(\omega t+\varphi \right)00\\ 04+4F^{\prime \prime \prime }\left(\frac{1}{4}\omega _1^2t^2\right)0\\ 0010+4F^{}\left(\frac{1}{4}\omega _1^2t^2\right)3\pi 𝐇_1\left(\omega _1t\right)8F^{\prime \prime }\left(\frac{1}{4}\omega _1^2t^2\right)\omega _1t\mathrm{sin}\left(\omega t+\varphi \right)\end{array}\right).\hfill \end{array}$$
(11)
Here

$$F^{}(z)={}_{1}{}^{}F_{2}^{}[\left(2\right);(\frac{1}{2},\frac{5}{2});z],F^{\prime \prime }(z)={}_{1}{}^{}F_{2}^{}[\left(2\right);(\frac{3}{2},\frac{5}{2});z],F^{\prime \prime \prime }(z)={}_{1}{}^{}F_{2}^{}[\left(1\right);(\frac{1}{2},\frac{5}{2});z],$$
(12)
$`{}_{p}{}^{}F_{q}^{}[𝐚;𝐛;z]`$ is the generalized hypergeometric function

$${}_{p}{}^{}F_{q}^{}[𝐚;𝐛;z]=\underset{k=0}{\overset{\mathrm{}}{}}\frac{\left(a_1\right)_k\mathrm{}\left(a_p\right)_k}{\left(b_1\right)_k\mathrm{}\left(b_q\right)_k}\frac{z^k}{k!},$$
(13)
where

$$\left(c\right)_n=c\left(c+1\right)\mathrm{}\left(c+n1\right)$$
(14)
is the Pochhammer symbol, and $`𝐇_n(z)`$ is the Struve function, which satisfies the differential equation

$$z^2y^{\prime \prime }+zy^{}+\left(z^2n^2\right)y=\frac{2}{\pi }\frac{z^{n+1}}{\left(2n1\right)!!},$$
(15)
where

$$n!!=n\left(n2\right)\left(n4\right)\mathrm{}$$
(16)
represents the double factorial.

This gives the powder average during the rf pulse. The terms proportional to $`\mathrm{sin}\left(\omega t+\varphi \right)`$ represent the quantum beats at the quadrupolar splitting frequency. In order to find the evolution after the pulse, we set the factors $`\omega _1t`$ to a constant corresponding to the phase accumulated during Rabi oscillation induced by the excitation pulse. In the results presented here, we set this constant equal to $`\pi /2`$. The only remaining time dependence is then in the $`\mathrm{sin}\left(\omega t+\varphi \right)`$ terms.


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# On the two principal curvatures as possible entropic barriers in a mesoscopic nonequilibrium thermodynamics model of complex matter agglomeration

## I Introduction

In this work, we wish to focus on a matter agglomeration process ranging in size of a constituting entity (grain; crystallite; cluster) between micrometer (physical metallurgical specimen or colloidal flock) and nanometer (biophysical agglomerate viz biomembrane) scales. The systems that we are going to address possess the following characteristic basic properties shvind

* They are diffusion–migration systems, which means that they are well–characterized by a diffusion process along the axis of their internal variable (volume, size, alike), and they undergo a kind of migration being recognized as a drift by capillary forces, provided that they are vitally present in the system hweaire ;
* The growing processes that are ’in action’, are of irreversible nature, so that a thermodynamic formalism is possible to apply mweaire ;
* The diffusion coefficient is proportional to the surface magnitude of a basic entity constituting the agglomerate under evolution, a physical scenario well–known mostly in colloidal agglomerations novikov ;
* The drift term is always proportional to the curvature: It turns out that it is either very related with the mean curvature, what is supposed to be true in physical–metallurgical systems being of micrometer size of its basic entity, or it appears to be identified with the Gaussian curvature, which can reasonably be judged as being characteristic of nanometer scale rather, in which (bio)polymeric agglomerations are supposed to be in favor, look at Fig. 1;
* The systems we examine always obey the local conservation law;
* They are constrained systems, mostly due to: (i) boundary conditons applied: they can be either of normal ($`0`$-Dirichlet) or of abnormal types mullins ; (ii) their total (hyper)volumes111Accept that the description considered is a space dimension ($`d`$)–dependent approach. which they can preserve (surface tension or elasticity effects pronounced) or cannot do it (no special role of surface tension assumed) liu . (Their evolutions, however, do not depend essentially upon the initial condition chosen.)

As the so-called case or exemplified study here, we wish to choose a physical–metallurgical process called normal grain growth the statistical theory of which can be found elsewhere. Its main characteristics can briefly be presented in the following way, see pande  and refs. therein:
(i) The polycrystalline evolution process takes place under a certain constraint concerning the constancy of the total system volume; (ii) It relies on evolution of grains constituting a specimen in such a way that the mean radius of the grains has to increase (the curvature(s) to diminish, automatically) while their total number has to decrease; (iii) An observed physical tendency while going over sufficient number of time spanes (decades) of the process is slowing down of the grain surface free energy in such a way that a possibly low surface free energy matter agglomerate is eventually obtained.

Put the above another way, let us follow C. S. Smith smith  who argued that normal grain growth results from a certain subtle, and recently re–examined mullins ; pande , interplay between topological viz geometrical (polygons–containing) or space–filling but random requirements as well as those of thermodynamic nature, preferentially due to surface tension agitation as well as elasticity–to–rigidity (bending) effects on the grain boundaries when the system really ”fights” to attain a local thermodynamic equilibrium under a set complex physico–chemical circumstances it meets on its way novikov .

Therefore, the role of curvature seems to us to be absolutely essential peczak . Because, however, of differences in the size of the main constituting entity (grain; cluster) within the classes of mesoscopic systems we want to examine, we see that for some bigger (coarse–grained, less elastic micrometer–scale) systems, as those metallurgical, the conception of the mean curvature would likely suffice to describe the system satisfactorily whereas for description of fine–grained assemblies (more elastic and less brittle nanosystems) the role of the so–called Gaussian curvature must be underscored agluczka . All the rationale we have just developed above finds its right as well as well–established place in some thermodynamic observations first published by Tolman tolman  who noticed that in certain fluid–like systems of suitable (appreciably small) size a size–dependent correction to surface tension improves its description. This led then to extensive studies of surface tension size–dependent effects in versatile Van–der–Waals as well as other systems bedo ; tolman .

Since the whole statistical–mechanical kinetic description of the grain growth of normal type (being a Fokker–Planck–Kolmogorov (FPK)–type description222In some literature called also a Smoluchowski or generalized diffusion approach.), or with uniform grain boundaries mullins  can be found elsewhere, we encourage a reader to consult niemiec ; agad1 ; agad2 . An important thing to mention here is that the corresponding grainy matter flux has been constructed in a phenomenological way therein agad1 , and that in it a standard–in–form diffusion (1st Fick’s law) term has been completed by a drift curvature - (capillarity) dependent term, just for reflecting properly the essential mechanism governing the presumably ordered agglomeration on many nuclei novikov ; mullins ; pande .

Very recently, another more improved way of constructing the matter flux has been proposed. It is based on dealing with a system undergoing normal grain growth as open thermodynamic system, and on applying the principles of nonequilibrium thermodynamics in the space of the grain sizes. (This proposal can also be extended on the time domain.) It immediately leads to express the entropy production, by the afore mentioned flux as well as by the adequate chemical potential gradient. The gradient, in turn, is to be defined by the chemical activity, $`a`$, being not equal to one for non–ideal systems, and by the physical potential, designated by $`\mathrm{\Phi }`$, that can be selected in a suitable form, conforming to physical circumstances we want to address, cf. micro– or nanometer–scale evolutions. The procedure just outlined can be found elsewhere rubi1 ; rubi2 ; rubi3 .

The article is structured as follows. In Section 2, we concisely describe a derivation of the flux of grainy matter, $`J`$, based on the nonequilibrium thermodynamics formalism, introduced very recently rubigad , briefly referring in the section’s beginning to the phenomenological construction proposed before agad1 ; agad2 . In the next two sections, Secs. 3, 4, respectively, we discuss two important physical cases leading to application of logarithmic as well as of Coulomb (or, gravitational) potentials, what refers to both afore mentioned micro– as well as nano–world evolutions within the agglomerating system under study agluczka . A final address and perspective (Sec. 5) complete our study on the entropic barriers in matter agglomeration.

## II Nonequilibrium thermodynamics derivation of a normal grain growth model

A procedure followed before agad1 ; agad2 ; agluczka  relied on proposing the flux of grainy matter yielding the agglomerate’s output in a phenomenological form rubigad

$`J(v,t)=\sigma v^{\alpha 1}f(v,t)Dv^\alpha {\displaystyle \frac{}{v}}f(v,t),`$ (1)
which implies essentially a decomposition into two parts. Here $`\sigma `$ and $`D`$ are surface tension as well as diffusion reference333The meaning of the word ’reference’ is the following here: $`\sigma `$, being a positive constant, corresponds to the surface tension of a flat interface (in consequence, the reciprocal of the flat interface radius, $`v^{\alpha 1}`$, gets zero, causing the drift term in Eq. (1) to vanish), whereas the constant $`D`$ is the diffusion coefficient taken from a standard–diffusion Einstein–like realization of the process in $`d=1`$, where the term $`v^\alpha =1`$, see Eqs. (1) and (2). constants, respectively, and in general $`\sigma D`$ is true; the internal state variable $`v`$ and an independent variable $`t`$ represent the volume of an individual grain as well as the time, respectively. $`\alpha `$ stands for a dimensionality $`d`$ (where $`d=1,2,3,\mathrm{}`$) dependent exponent agad1

$`\alpha ={\displaystyle \frac{d1}{d}},`$ (2)
i.e. it is presented in a fractional form, namely, by providing a ratio of the subdimension $`d1`$ and the space dimension $`d`$. (This can be thereafter referred to as a surface–to–volume exponent; notice that when $`\sigma =\alpha `$ holds, one arrives at a standard description of normal grain growth by Mulheran and Harding, whereas for $`d=1`$, one gets $`\alpha =0`$ ($`\sigma =0`$), and a purely diffusive description of possibly ordered agglomeration by Louat, cf. niemiec ; agad1 ; agad2 ; rubigad , and refs. therein.) The first part of the right-hand side (r.h.s.) of Eq. (1) is a drift term. The second part of the r.h.s. of Eq. (1) stands for a diffusion term. The former is a capillary term, proportional to the (mean) grain curvature, and much involved in the Laplace–Kelvin–Young law, so much explored for crystallites–containing systems novikov ; agluczka . The latter is simply the first Fick’s law, and it underscores a proportionality of the flux to the grain surface magnitude. Both the terms incorporated in (1) are based on phenomenological laws, so is, without doubt, the construction of the mixed convection-diffusion local flux (1), supplemented here by (2) being of geometrical meaning. Bear in mind here that via a relation $`vR^d`$ ($`R`$ \- a grain radius) in the drift term one really provides $`v^{\alpha 1}R^1`$ (see, Eq. (2)), which means, that a curvature term can easily be revealed this way. In the diffusion term, in turn, one clearly gets a surface term $`R^{d1}`$ since $`v^\alpha R^{d1}`$ when $`vR^d`$ is applied again.

After stating explicitely the flux, we have to apply it to the local continuity equation

$`{\displaystyle \frac{}{t}}f(v,t)+{\displaystyle \frac{}{v}}J(v,t)=0,`$ (3)
where $`v`$ is the volume of a grain, $`f(v,t)`$ is the distribution function of the grains at time $`t`$ (having a meaning of the number density, but being unnormalizable niemiec ; agad1 ), that means, $`f(v,t)dv`$ is a relative number of grains of size in the volume interval $`[v,v+dv]`$.

The overall conceptual and mathematical construction is to be completed by suitable initial and boundary conditions. A general observation is, however, that the process in question does not depend upon any prescribed initial condition, cf. niemiec . After a sufficient time interval being overcome it completely forgets its initial state pande .

This is not the case of the boundary conditions (BCs), however. The process visibly depends upon BCs prescribed. A choice that remains as most explored is the choice of zero Dirichlet BCs, namely $`f(v=0,t)=f(v=\mathrm{},t)=0`$. (Realize that the BCs–proposal may not work in a semi–infinite phase space, $`v[0,\mathrm{}]`$; another use of BCs can lead to some inconsistency, because the volume of an individual grain can be large and can even be larger than the overall volume of the system, cf. discussion in agluczka ; niemiec ; rubigad .)

There is some physics staying behind the BCs: The grains of zero as well as of infinite sizes have zero account for the grain growth. This physical constraint is sometimes called a normality condition, and the process is supposed to be normal when the above is true. Otherwise, one may name the agglomeration abnormal novikov .

Suppose that we are still interested in a construction procedure of the flux $`J(v,t)`$, hopefully arriving at a form reminiscent of that of Eq. (1). It is worth doing, first, because the phenomenological way gives us no full satisfaction and/or control, and second, that we wish to have a more sophisticated procedure staying behind the derivation, with possible open ways for application as well as more versatile examination of the polynuclear agglomerations. So, we realize that another non–phenomenological method will be applied therein though we will be not capable of avoiding phenomenology totally rubigad . We will, however, be capable of arguing quite firmly and in a physically reasonable as well as quite general way on the basic mechanism of the agglomeration in the spirit of incorporating (or, having not incorporated) the suitable entropy barrier as a geometrical one rubipre , here inevitably associated with the principal grain curvatures. Another, more explicit as well as presenting really state of the art (geometry) way has been shown in rubipre , and via a Random Walk (RW)–analogy invoked below, can be adopted in a future task for deriving specific geometry-dependent forms of the physical potentials upon request.

Thus, assume that the continuity equation (3) is still the proper evolution equation for the agglomerating system but the flux $`J(v,t)`$ remains to be specified. Assume, moreover, that there is a method of deriving it, and that the method is called mesoscopic nonequilibrium thermodynamics rubi1 ; rubi2 . It starts with the Gibbs equation which represents the entropy variations, namely rubi1 ; rubi3

$`\delta S={\displaystyle \frac{1}{T}}{\displaystyle \mu (v,t)\delta f𝑑v},`$ (4)
where $`ff(v,t)`$, $`T`$ is the temperature, and $`\mu (v,t)`$ is the chemical potential in $`v`$-space. The latter is given by (here, $`\mu \mu (v,t)`$ for a brief notation is taken)

$`\mu =k_BTln(af),`$ (5)
where $`aa(v)`$ is an activity coefficient reflecting the fact that the system is not ideal; for $`a=1`$ it would become ideal. (Bear in mind that the $`ln`$–form of the chemical potential suggests the system were ideal but, fortunately, the condition $`a1`$ would likely violate the presupposed ideality.) $`k_B`$ is the Boltzmann constant. Next, $`a`$ is given in terms of a potential that for the reason of a clear differentiation against the chemical potential $`\mu `$ let us call the physical potential, $`\mathrm{\Phi }`$. $`a`$ reads now rubi1 ; rubi2

$`a=e^{\mathrm{\Phi }/k_BT}.`$ (6)
Providing the temporal derivative in Eq. (4) and partially integrating (assuming, additionally, that $`JJ(v,t)`$ vanishes at the ends of the phase space), one gets the entropy production, $`\sigma _E`$, in $`v`$-space

$`\sigma _E={\displaystyle \frac{1}{T}}J{\displaystyle \frac{\mu }{v}}`$ (7)
from which we may easily infer the expression for the grainy flux

$`J={\displaystyle \frac{1}{T}}L(v){\displaystyle \frac{\mu }{v}}.`$ (8)
(Here, we have assumed that the process is local in $`v`$; one would also consider, if necessary, a non–local case by $`J(v)=\frac{1}{T}𝑑v^{}L(v,v^{})\frac{\mu }{v^{}}`$, cf. rubi1 ; rubi2 .) Combining Eqs. (8), (5) and (6) one gets

$`J={\displaystyle \frac{1}{Tf}}L(v)\left[k_BT{\displaystyle \frac{f}{v}}+f{\displaystyle \frac{\mathrm{\Phi }}{v}}\right].`$ (9)
Now, let us define the mobility $`b(v)`$ as $`b(v)=\frac{1}{Tf}L(v)=\frac{D}{k_BT}v^\alpha `$, where $`D`$ and $`\alpha `$ are stated as above.

The derived flux $`J`$ is given by

$`J=Dv^\alpha {\displaystyle \frac{}{v}}fb(v)f{\displaystyle \frac{}{v}}\mathrm{\Phi }.`$ (10)
The obtained expression, viz Eq. (10), looks quite general, probably inspite of the power–law form (grain–volume correlations) assumed in the Onsager coefficient $`L(v)`$. The main physics to anticipate now is to propose a valuable expresion for the physical potential $`\mathrm{\Phi }=\mathrm{\Phi }(v)`$. This is, however, a matter of offering a principal agglomeration mechanism for the system(s) to evolve. A proposal for a micrometer– kurz  as well as nanometer– rubi3  sized evolutions, respectively, will be provided in the two subsequent sections.

## III Matter agglomerations in micrometer–world

Our first proposal is to make use of that there is a possibility of including an above announced geometrical barrier when a non–power (here, logarithmic) form of the potential $`\mathrm{\Phi }=\mathrm{\Phi }(v)`$ is presumed rubigad . We see that the way of doing it is worth going, see Introduction. This is generally because of the well–known Tolman correction in curvature performed for the surface tension of a ”droplet” of radius $`R`$, namely $`\sigma 1(\delta _T/R)`$, where $`\delta _T`$ stands for the Tolman length. Such a correction procedure, going to predict a decrease of the surface (line) tension for sufficiently small objects, leads also to an inclusion of (twice) the mean curvature (the entire thermodynamic context assumes the Gibbs–Thompson or capillary length, $`\delta _{GT}`$, to be a characteristic length of surface or line tension shrinking actions) of a curvature–driven grain growth and phase separation mechanism hillert  whereas the so–called second correction, just related with the Tolman length, $`\delta _T`$ tolman ; bedo , and termed the Gaussian curvature, reveals certain elastic (towards elasticity/rigidity, and the bending effect) properties of an agglomerate’s grain surface in a time instant chosen, and when going over its evolution stages, in which such characteristics can vary.

Thus, the proposed non–power form of the physical potential is of a logarithmic form, namely

$`\mathrm{\Phi }=\mathrm{\Phi }_oln(v/v_o),`$ (11)
where $`v_o>0`$ stands for the initial grain volume. Interestingly, exactly this form suits very well to what we want to get. The entire rationale we try to reveal thoroughly, mostly below, is that we wish to have in the drift term, present in either Eq. (1) or Eq. (10), a factor of $`v^{\alpha 1}`$ which is explicitely a clear signature of the curvature, being a reciprocal of the grain radius $`R`$, see Sec. 2. Thus, after simple algebra $`\frac{}{v}\mathrm{\Phi }=\mathrm{\Phi }_o\frac{1}{v}`$, we are able to recover the desired form of the drift term in flux (1), and this way both the fluxes, (1) and (10) take firmly on the same mathematical form, presumed that $`\alpha `$ is that dimensionality–dependent fractional number taken from (2), called above the surface–to–volume exponent. To have a really entropic barrier an additional demand on explicit dependence of the prefactor $`\mathrm{\Phi }_o`$ upon the thermal energy $`k_BT`$ is needed, as applied for certain (star) polymeric complex solutions, for example waclaw , carrying however less about that their logarithmic part of the potential is distance–dependent, whereas ours explicitely not, cf. Eq. (11). (We may have some excuse here by realizing again that $`vR^d`$, where $`d`$ as above, and the radius $`R`$ can likely better mimic a distance, or a position measure than $`v`$ does.)

Another issue that can be addressed seems more fundamental. It concerns our analogy between the RW in a position space and the walk along the grain size axis agluczka ; agad2 , see also beginning of Sec. 2. There are some experimental evidences kurtz  as well as theoretical predictions pande ; agluczka  (look at refs. therein) that the walk in grain–size space would belong to a broad class of geometric Brownian motion (a Wiener processs), the probability distribution of which is a logarithmic Gaussian agluczka . Thus, instead of $`v`$ in the mathematical form of the Gaussian distribution a $`ln(v)`$ must appear as argument. Therefore such a potential seems legitimate too. (A certain analogy between the mass–exchange action between neighboring grains mullins  of a polycrystal, in which one of them is active, or ’waken’, in transferring matter from its neighbor’s volume via the grain boundary while the remaining one ’sleeps’ when doing it, and the RW in a $`ln`$–potential, modeling sleep–wake dynamics during sleep stanley .)

Accepting that the key problem, because of the RW-analogy in both the spaces mentioned, does not totally rely on whether we have $`v`$ or $`R`$ in potential function argument, i.e. a distance measure in (11), we may at least for a two-dimensional case, invoke another experimental study with a logarithmic potential. The study is on a confined mesoscopic system in which the so–called Wigner islands emerge. These are charged balls interacting via an electrostatic potential wigner . They represent the vortices in type-I superconducting systems. It turns out that just the logarithmic interaction potential causes maximum compaction of the charged spheres of milimeter, viz macroscopic size, usually moving and agglomerating on a conductor plane wigner . This is thus probably no surprise that the $`ln`$–potential (11) but not a power–like, for example, gives more chances for the system to advance into a constant total volume regime as the system growing under normal conditions agluczka ; agad1  does. This is, as is stated in Sec. 2, the case when the governing mechanism based on (mean) curvature driving prevails, and in which a surface (line) tension effect cannot be avoided.

In rubi1  it was shown that diffusion as well as mobility functions are very related to each other. They are also related with the Onsager coefficient $`L(v)`$ via the grain (cluster) distribution function $`f`$, or also via an inclusion of the temperature $`T`$ as is in the case of mobility, and does not apply for the diffusion coefficient.

The diffusion coefficient, in its full form denoted by $`D(v,t)`$, is generally assumed to be defined by the Green–Kubo correlation formula, taken from the fluctuation–dissipation theorem, in which, as the integrands, random parts, $`J^r(v,t)`$, of the flux (10) of grainy matter are involved. It is given by $`D(v,t)=\frac{k_B}{f}L(v)=Dv^\alpha `$, which means that algebraic correlations are assumed in the correlator based on the $`J^r(v,t)`$ rubi1 ; rubi3 . (Some correlation in time domain are plausible too, mostly for describing agglomerations in soft–matter reactive systems viz biomembranes here jamnik .)

Since it has been argued mullins  (see, literature therein), and experimentally proved kurz , that the normal grain growth processes are self–similar in many respects and when based on quite many versatile measures of self–similarity both in space (grain size) and time, it would be useful to test this observation within the framework of our modeling. It is done in the subsequent section by proposing another potential $`\mathrm{\Phi }=\mathrm{\Phi }(v)`$ being generally of the Lennard–Jones (LJ) form.

## IV Matter agglomerations in nanometer–world

Our second proposal on how to perform a model agglomeration is to assume, inspite of the algebraic (self–similar–in–time) correlations $`<J^r(v,t)J^r(v^{},t^{})>`$ of the flux $`J^r(v,t)`$ rubi1 , that also the physical potential is of a power form in $`v`$

$`\mathrm{\Phi }={\displaystyle \frac{\mathrm{\Phi }_1}{v^{ϵ_1}}}+{\displaystyle \frac{\mathrm{\Phi }_2}{v^{ϵ_2}}},`$ (12)
where $`\mathrm{\Phi }_i`$ ($`i=1,2`$) are constants (they may depend upon temperature, and as suggests the construction of the LJ–potential, they must be of opposite signs so that we choose here $`\mathrm{\Phi }_1<0`$, i.e. the attractive part of the LJ–potential has to be taken with minus sign, so that the Van der Waals–like attraction for preserving agglomeration is desired), and $`ϵ_i`$ ($`i=1,2`$) are positive exponents.

We have now to perform partial differentiation, $`\frac{}{v}\mathrm{\Phi }`$, and put the resulting expression into Eq. (10), which gives

$`J=Dv^\alpha {\displaystyle \frac{}{v}}f\sigma _1v^{\chi _1}f\sigma _2v^{\chi _2}f,`$ (13)
where: $`\chi _1=\alpha ϵ_11`$, $`\sigma _1=\mathrm{\Phi }_1ϵ_1\eta ^1`$; $`\chi _2=\alpha ϵ_21`$ and $`\sigma _2=\mathrm{\Phi }_2ϵ_2\eta ^1`$; here $`\eta ^1=\frac{D}{k_BT}`$, is the inverse of a viscosity. This way, we get the grainy matter flux (1), or strictly speaking (10), in a very satisfactory form. A direct comparison with (1) from Sec. 2 provokes to let $`ϵ_i0`$ ($`\chi _i\alpha 1`$) which yields $`\mathrm{\Phi }const`$ (very weak forces as the Van der Waals normally are!). Thus, the flux (13) is really in the form we await very much except that the very fact that both the surface tension reference constants $`\sigma _i`$ ($`i=1,2`$) unfortunately tend to zero, cf. the formulae below Eq. (13). In this way, the drift term is completely removed, and we get no drift effect on the agglomeration. Thus, an entropic barrier due to curvature cannot be proposed based on such an oversimplified argumentation. (Notice, by the way, that in our geometry–dependent model, cf. agad2 ; jamnik  and refs. therein, the prefactor appearing in the drift term of Eq. (1) is a kind of curvature–including over–constraint always present in our thermodynamic model, recall that $`v^{\alpha 1}R^1`$, see again Eq. (1) as well as Eq. (2).)

Let us try, however, another way to put things forward. Let us take that there exists a mutual dependence between $`\chi `$–s. It is likely to be proved while looking at standard forms of LJ– (or, $`612`$–potential) as well as LJ–like (for instance, $`1012`$–potential, used in modeling some presence of $`H`$–bonds in protein assemblies, see cieplak , and refs. therein) potentials. We see for them a simple mutual dependence between $`ϵ`$–s, for instance $`ϵ_2=2ϵ_1`$ for the $`612`$–potential. Or, $`ϵ_2=(6/5)ϵ_1`$ just for the $`1012`$–potential. But exploration of such a simple algebraic ”correlation” makes no sense since, as mentioned above, always $`\sigma `$–s will go to zero. In other words, there is no reason to get on the problem when staring from the potential’s form directly.

It is, however, worth exploring here a sort of mutual dependency between $`\chi `$–s, that means, when starting from the level of the flux (13). It can be proposed as a systematic but very simple algebraic procedure, and can be done as follows. Namely, let us first recall that both $`\chi `$–s are of the form

$`\chi _i=(\alpha 1)ϵ_i,i=1,2,`$ (14)
but notice that they cannot equal one another. In consequence, let us assume a simple linear relation

$`\chi _2=q_\chi \chi _1,`$ (15)
where $`q_\chi 1`$, and clearly $`q_\chi 0`$. After simple algebra, by making use of the equality (15) as well as applying (14), one gets

$`ϵ_1=(ϵ_2/q_\chi )+(1q_{\chi }^{}{}_{}{}^{1})(\alpha 1)`$ (16)
or, equivalently, one can provide $`ϵ_2=ϵ_1q_\chi +(1q_\chi )(\alpha 1)`$ but we choose the case of $`ϵ_1`$ for further consideration.

By letting $`ϵ_20`$ we wash out completely the term with $`\sigma _2`$ in Eq. (13), but we still have a nonzero $`ϵ_1`$ that reads in such a limiting case as follows

$`ϵ_1=(1q_{\chi }^{}{}_{}{}^{1})(\alpha 1).`$ (17)
This exponent for a possible choice of $`q_\chi =1/2`$ ($`q_\chi `$ carries this way some signature of the second curvature correction, by the way) gives in Eq. (13) a term which looks like $`v^{2(\alpha 1)}`$, what again via $`v^{2(\alpha 1)}R^2`$ results in appearence of a second curvature (Gaussian) term, being proportional to $`1/R^2`$ bedo ; tolman ; hweaire . This term must clearly be of importance for sufficiently small grains–containing systems, and we argue that it may happen in the nanometer scale novikov . Crudely speaking, it looks like the evolution in micrometer scale goes on more likely in a logarithmic fashion ($`ln`$–potential) than algebraically. (The size of the basic entity constituting an agglomerate is not very much emphasized in micrometer scale.) The latter, in turn, is much pronounced in nanoscale because of apparently small size of the basic constituting entity: In this physical scale, however, a LJ–like potential is very likely to be in favor, cf. the above argumentation.

In nanoscale, cf. Eq. (12), the form of $`\mathrm{\Phi }`$ is the following

$`\mathrm{\Phi }(v)=\mathrm{\Phi }_2+{\displaystyle \frac{\mathrm{\Phi }_1}{v^{(\alpha 1)}}},`$ (18)
what in terms of the distance (or, linear size) $`R`$ results in

$`\mathrm{\Phi }(R)=\mathrm{\Phi }_2+{\displaystyle \frac{\mathrm{\Phi }_{11}}{R}},\mathrm{\Phi }_{11}<0,\mathrm{\Phi }_2>0,`$ (19)
and $`\mathrm{\Phi }_{11}`$ is a constant closely related to $`\mathrm{\Phi }_1<0`$.

For a microscale description, but given in terms of $`R`$, one provides the potential $`\mathrm{\Phi }(R)`$ as

$`\mathrm{\Phi }(R)=\mathrm{\Phi }_{oo}ln(R/R_o),`$ (20)
where $`\mathrm{\Phi }_{oo}`$ is a constant staying again in close relation to $`\mathrm{\Phi }_o`$, whereas $`R_o`$ looks like an initial grain radius. Certainly, Eq. (11) is a $`v`$–containing counterpart of the above, see Sec. 3.

Of utmost importance appears to be the understanding of how does the grain boundary (cluster peripherial area), that is going to mimic an interface (here, between contiguous grains, or clusters, of possibly different internal structural architecture) curve, and upon which physical circumstances does it really go? There are two possible thermodynamic routes proposed in such a situation, namely bedo2 :
(i) the one, based on how does an equilibrium interface curve due to a chemical gradient change just on the grain boundary interface,
(ii) another one, that undergoes nonequilibrium thermal fluctuations.
Both the routes mentioned above seem to be plausible within the presented agglomeration context, though the scenario drawn must always depend solely upon concrete physical mechanism applied shvind ; novikov ; mullins . Though the route (i) cannot be discarded á priori for our agglomeration context as a whole, it looks more safely applicable to microagglomeration driven by non–LJ potentials and forces as in some metallic as well as thin–film ceramic czekaj  systems, e.g. in relaxor multicomponent materials skulski . The route (ii), in turn, is readily supported by the LJ–force–and –potential context as in soft–matter systems novikov ; cieplak ; earnshow , e.g. in micellar droplets and biomembranes for which both theoretical (Kirkwood–Buff approach) napior  as well acurate numerical stecki  evaluations of the rigidity constant, associated with the Gaussian curvature effects on a membrane surface, predict its value to be negative, and the interactions have been assumed to be of LJ–form bedo2 , so that, according to our rationale, we have to be placed now within the nanoagglomeration context. This is, thus, another evidence that the Gaussian curvature is related with the LJ–context, and vice versa. The route (ii) suits very well to highly fluctuating ordered agglomerations in biopolymeric complex soft–polycrystals ag , for which the surfaces of the grain boundaries, denoted by $`s_{d=3}`$, fluctuate with the time $`t`$ as $`s_{d=3}t^2`$ for $`t>>1`$ again, cf. ag  and the discussion between formulae (14) and (15) therein.

Finishing this section, it is worth mentioning that both the forms derived above in terms of a distance measure $`R`$, Eqs. (19) and (20) respectively, are physical–potential forms well–known, e.g. in electrostatics: The former represents a far–distance electrostatic potential, emerging from an electric point charge, whereas the latter is expected for extremely long cylindrical (presumably, torus–like) capacitors in which internal cylinder is charged oppositely (for example, negatively) to its external cylindrical (positive) counterpart. A qualitative observation can be offered, namely, that here a tube–like structure of the capacitor recalls somehow the capillarity effect, which prevails in the microworld but would not be a decisive phenomenon in its nano–counterpart. ¿From the textbooks on electrostatics it can be learned that both the prefactors present in the inverse–power term of (19) as well as in (20) should, in a material medium, contain the dielectric constants of the medium they are made of. It belongs, in turn, to a standard knowledge on the principles of biomolecular physics, that, if the dielectric constant enters into a description of interactions, like in ligand–protein or other bio–complexes, or agglomerates of them, there is a good opportunity to advocate for an explanation that the entropy change (but not its enthalpic counterpart) might have the foremost influence on the agglomeration process. Therefore, we are privileged to call, even without going into details, the entropic barriers, being represented by the curvatures, as potentials, causing the entropy change in the agglomerating system under study. For a typical interacting biomolecular system the entropy contribution under normal temperature conditions around $`T298K`$ is usually about $`34`$ times larger than the enthalpy contribution can be, though they can be of opposite signs, with a preference about a positive value for the entropic term, however. Certainly, a formal analogy may also be extended for the gravitational objects driven by the corresponding central forces that are based on the potentials (18) and (11), respectively. As for the logarithmic potential, one may also found an appealing analogy in biomemebrane science between a system consisting, e.g. of a lyposome (vesicle) with a small colloid attached, having a common logarithmic contour (catenoid) that would resemble an equipotential surface of the system mentioned, cf. helfrich , and refs. therein. Such a scenario is reminiscent of our grains–containing agglomeration in which, on a microscopic level, a small grain is being attached to its bigger neighbor, being absorbed thereafter, preferentially because of the action of capillarity shvind ; mullins ; pande . The two curvatures mentioned constantly throughout the paper are of importance in both the situations described helfrich ; pande ; mullins ; niemiec ; peczak .

## V Final address and perspective

The final address, and a perspective towards how to possibly deal with it further, can be split up in the following:

* To sum up: We have applied mesoscopic nonequilibrium thermodynamics rubigad  in order to improve a phenomenological $`d`$–dependent construction agad1 ; agad2  of the grainy matter flux given finally in Sec. 2 by Eq. (10), and proposed to describe an ordered agglomeration, termed the normal grain growth mullins .
* When offering such an improvement we have realized that we have either to calculate explicitely the form of the correlations of the random part of grainy flux rubi2 ; rubi3  by relying on a physical mechanism, proposed for such a purpose, or to assume a (physically natural) geometrical constraint by keeping the surface–to–volume exponent effective, see Eq. (2). It enables then to realize that the (mean) curvature has to be a principal geometrical constraint, cf. Eqs. (1) and (10).
* It has remained to note that in ”hard” condensed–matter systems mullins ; pande , mostly, the curvature, or a simple reciprocal of the grain radius, would sufficiently support the description of the system evolution. In soft condensed–matter agglomerates, in turn, operating most effectively in nanoscale (see, Fig. 1), the Gaussian curvature, being a reciprocal of $`R`$ squared, as well as the Tolman correction to surface (line) tension, emphasized above, are just the case peczak ; shvind . (By emphasizing the role of both the curvatures a kind of crossover between the nano– as well as microscales can be addressed as well.) It would then be a serious candidate for supporting the overall evolution strategy already described.
* The forms of the proposed physical potentials $`\mathrm{\Phi }`$ are then offered twofold: Either in a logarithmic form (11) or as a sum of two power–like forms (12). Though a choice of the potentials known in physics is pretty vast stauffer , we have exactly picked up those two forms because they not only follow well the relatively simple mathematics staying behind the model rubigad ; niemiec  but above all they suit extremely well to the offered physical scenarios of agglomeration; in this moment, let us state clearly that, perhaps, except for entering the region of very small inverse Debye length values (high temperature limit or small co– and counter–ion concentrations), we see now no direct chances for applying here readily the frequently mentioned DLVO physical potential (screened Coulomb) so well applicable to most of colloid as well as surfactants–containing systems hansen ; stauffer . This is maybe therefore that it describes mostly repulsion effects but for preserving agglomeration we undoubtedly need attraction too hansen . (By the way, if we assume $`\mathrm{\Phi }`$ to be given by a single power form we will be unable to recover the Gaussian curvature mechanism at all rubigad .)
* The normal grain growth model mullins ; pande ; hillert  is a model in which agglomeration is being realized in a random fashion and under a space–filling constraint agad2 . It is well–known agad1 ; niemiec  that for it the kinetic dependence of a mean grain radius is given by $`Rt^\nu `$ ($`t>>1`$), where $`\nu =1/(d+1)`$, i.e. the exponent is given by a reciprocal of the superdimension $`d+1`$. Interestingly, the model with a surface–to–volume exponent $`\alpha `$ assumed, which clearly invokes colloidal agglomerations earnshow , see Eq. (2), yields an asymptotic kinetic law constituted by the superdimension $`d+1`$. But it seems natural: the $`d+1`$–account is just a proper description of nearest neighborhood for a grain in $`d`$–dimensions agad2 ; the whole matter agglomeration strategy is sometimes termed in textbooks the random close–packing. Therefore, such a kinetic law seems legitimate as well niemiec ; agad1 .
* The above is going to be a bit changed for the nanoworld for which a kinetic law may change, presumably as $`Rt^\omega `$ ($`t>>1`$), where $`\omega =1/(d+2)`$ could be predicted here. Thus, the evolution goes slower. There is an evidence that such a slowing down of the grain–growth rate may emerge, for instance in some specially fabricated (cryomilled; then kept in about $`2/3`$–regime of melting temperature) nanopowders, and mostly due to pinning effects, accompanied by precipitation sub–effects at grain boundaries, presumably giving room for Gaussian–curvature assisting, or bending, phenomena to enter riso . Moreover, both the models, with the mean as well as the Gaussian curvatures, are quite reminiscent of a ”hydrodynamic” pairwise coalescence (ripening; clustering) model proposed in the early seventies by Binder and Stauffer, in which however, the diffusion process is really done in a position space, being as in our model, composed of two (other) parts: a translational as well as some rotational, cf. furukawa , and refs. therein. The kinetic radius vs time law was obtained the same furukawa , and the cluster–interaction parameter inferred from Binder and Stauffer’s formulae, say $`\iota `$, obeys: $`\iota =d1`$ (the subdimension) for the microworld evolution, whereas $`\iota =d`$ (the Euclidean dimension) for nanoagglomeration, both of them being exhaustively described in the present article in terms of a nonequilibrium thermodynamics model with geometric constraints. By the way, note that $`\alpha `$ of Eq. (2) just combines again both $`\iota `$–s mentioned above.
* A general observation appears that anticipates the agglomeration process as being accelerated (mean curvature mechanism) or decelerated (Gaussian curvature mechanism) by presence of such entropic, kinetic–geometric, barriers; moreover, presence of the drift term in Eq. (1), or equivalently in Eq. (10), makes the agglomeration more directional viz ordered. In all the cases mentioned the role of surface tension is to be emphasized, but its possible neglect, characteristic of loosely agglomerating systems lutz  (ripening; cluster–cluster aggregation mullins ; novikov ; earnshow ), leads also to the same $`d+1`$–account in the growth law because in late time regimes the role of capillarity, according to the frequently addressed Laplace–Kelvin–Young law, is not very much underlined, and therefore the asymptotics of both the systems, with and without visible capillarity influence, look the same niemiec ; lutz ; hillert .
* Some possible future task remains to solve formally the LJ–potential influenced system (with the Gaussian curvature mechanism, including $`v^{2(\alpha 1)}`$–term)

$`{\displaystyle \frac{}{t}}f(v,t)+{\displaystyle \frac{}{v}}J_G(v,t)=0,`$
where

$`J_G(v,t)=\sigma v^{2(\alpha 1)}f(v,t)Dv^\alpha {\displaystyle \frac{}{v}}f(v,t),`$
with appropriate initial as well as boundary conditions as it was already done for its $`ln`$–potential influenced counterpart niemiec ; agad1 ; lutz ; agad2 ; rubigad . (But it is left for another study, preferentially for $`d=3`$, i.e., $`\alpha =2/3`$, which is physically a more transparent as well as quite common case hweaire ; novikov .) Moreover, it is possible to consider other, higher order (above 2nd order), accounts to curvature, what has already been done for single–crystal growth from either supersaturated solution or undercooled melt kessler ; agluczka . For example, for $`q_\chi =1/3`$ a third curvature correction, like $`1/R^3`$, responsible for asymmetric growth kessler , may emerge. (Higher curvature ”modes” of the growing process444In general, the distance–dependent potential $`\mathrm{\Phi }(R)`$ would consequently obey: $`\mathrm{\Phi }(R)Const.+R^{(n1)}`$ for $`n>1`$ and natural, where $`n`$-s enumerate the subsequent curvature modes., like $`q_{\chi }^{}{}_{}{}^{(n)}=1/n`$, where $`n>3`$ here (and certainly natural), would also be responsible for some other nonlinear, and quite numerous effects, arising possibly during growth in complex materials shvind ; rubi3 ; novikov ; peczak ; kessler . Some of the effects predicted, may advocate for superplastic behavior of the model agglomerates just considered. It turns even out that effect of superplasticity can more likely be attributed to nanomaterials because they, compared to micromaterials, are composed of smaller, and possibly more curvilinear grains for which cohesion effects are rather more pronounced agluczka ; grabski .)
* It is also worth examining the proposed evolution equations in terms of a fractional FPK–dynamics metzler  because of its better sensitivity to different short, intermediate and long time–scale events jamnik  in nucleation–and–growth phenomena, leading quite often to formation of model biomaterials and/or biomembranes (microemulsions, too); till now it was proposed to be solved phenomenologically by postulating the corresponding but full space– and time correlations in $`D(v,t)`$, being of a power form, cf. jamnik . Then, some attempts of applying standard derivatives, not the fractional ones, but for a finite agglomerating system, and with fractional statistical moments of the examined growing process, have recently been started too agluczka .
* An open question remains whether so described agglomerations are supposed to be named orderly agglomerations? Clearly, on the basis of the proposed mesoscopic mechanism, involving a stochastic variable $`vv(t)`$ and no formal constraints as for preserving an order within the evolving system (the total volume, being constant, is surely not enough here), we cannot judge unambigiously whether the agglomeration, in either the microscale or in its nano–counterpart, proceeds orderly, or not. But, at least for bioagglomerations, i.e. the matter agglomerations involving a biomaterial, we can state so: Once an evolution way is selected by a system more or less at random (the initial state), then this selected random formation goes via a possibly efficient (self-organized; minimum–energy cost) way blumen . If an unordered system is met randomly, in turn, the evolution can then be named as unordered. (It may, however, be slightly improved in the course of the evolution but one cannot expect drastic, here ordered, changes, without applying equaly drastic viz decisive external stimuli.)

Last but not the least, it is clear that the proposed theory of matter agglomeration is thought of to be an extension of the (normal) grain growth theory unquestionably suitable for pure single phase systems, in which the kinetic parabolic law is mostly expected to occur atkinson , whereas in our approach it looks like an exception riso , being realized exclusively for $`d=1`$ ($`\alpha =0`$), i.e. for the one–dimensional reference state agad1 , see Sec. 2.

## Acknowledgement

Thanks go to Prof. K. J. Kurzydłowski (Warsaw University of Technology) and Mr. Jacek Siódmiak (University of Technology and Agriculture, Bydgoszcz) for reading a preceding shortened version of the manuscript as well as the present manuscript, respectively.


text:
# Phase Modulated Thermal Conductance of Josephson Weak Links

## Abstract

We present a theory for quasiparticle heat transport through superconducting weak links. The thermal conductance depends on the phase difference ($`\varphi `$) of the superconducting leads. Branch conversion processes, low-energy Andreev bound states near the contact and the suppression of the local density of states near the gap edge are related to phase-sensitive transport processes. Theoretical results for the influence of junction transparency, temperature and disorder, on the phase modulation of the conductance are reported. For high-transmission weak links, $`D1`$, the formation of an Andreev bound state at $`ϵ_\text{b}=\mathrm{\Delta }\mathrm{cos}(\varphi /2)`$ leads to suppression of the density of states for the continuum excitations that transport heat, and thus, to a reduction in the conductance for $`\varphi \pi `$. For low-transmission ($`D1`$) barriers resonant scattering at energies $`ϵ(1+D/2)\mathrm{\Delta }`$ leads to an increase in the thermal conductance as $`T`$ drops below $`T_c`$ (for phase differences near $`\varphi =\pi `$).

The Josephson effect in superconducting weak links is perhaps the best known example of macroscopic phase coherence. In addition to the superconducting tunnelling current, $`j_s=j_c\mathrm{sin}\varphi `$, Josephson Josephson (1962) showed that the electrical current through a tunnel junction includes Ohmic terms, $`j_d=(\sigma _0+\sigma _1\mathrm{cos}\varphi )V`$, where $`\varphi `$ is the phase difference between the two superconductors, and $`V`$ is the voltage across the junction. These terms describe dissipative quasiparticle tunnelling when the junction is biased by a voltage. The term, $`\sigma _1V\mathrm{cos}\varphi `$, is attributed to “interference” between Cooper-pair and quasiparticle tunnelling Josephson (1962); Harris (1974); Langenberg (1974), and averages to zero in voltage-biased junctions.

Phase-modulated dissipative currents are characteristic of any type of superconducting weak link. For example, the thermal current through a temperature-biased SIS junction is predicted to be a periodic function of $`\varphi `$ Maki and Griffin (1965). For a stationary phase difference the thermal conductance is also stationary. Thus, in contrast to voltage-biased junctions, the phase-modulated thermal conductance does not average to zero. However, less is known about phase-sensitive thermal transport across superconducting weak links compared with their current-voltage characteristics. Recent investigations of heat transport through SIS junctions are based on the tunnel Hamiltonian method Guttman et al. (1997), while Kulik and Omel’yanchuk Kulik and Omeĺyanchuk (1992) calculated the thermal current for the opposite extreme of a perfectly transmitting superconducting constriction (a “pinhole”). In terms of the transmission coefficient of the interface potential barrier between two superconductors, the SIS junction corresponds to $`D1`$, while the pinhole corresponds to perfect transmission, $`D1`$.

In the following we present a theory for quasiparticle heat transport through superconducting point contacts for any junction transparency, and as a function of temperature and disorder. The thermal conductance is sensitive to spatial inhomogeneities of the order parameter, particularly changes in phase, which lead to branch conversion between particle- and hole-like excitations Andreev (1964), and to the formation of low-energy bound states in the vicinity of the point contact. The bound state spectrum and transmission probabilities for continuum excitations are strongly modified by the junction transparency, which leads to large changes in the thermal conductance of the junction.

To study quasiparticle transport through temperature-biased superconducting weak links, we use the method of nonequilibrium quasiclassical Green functions Eschrig (2000). In this formalism the advanced and retarded Green functions, $`\widehat{𝔊}^{A,R}`$, describe the local spectrum of excitations for the system, while the Keldysh Green functions, $`\widehat{𝔊}^K`$, carry the information about the nonequilibrium population of these states. Each propagator, $`\widehat{𝔊}^{A,R,K}(𝐩_f,ϵ;𝐑,t)`$ is a $`2\times 2`$ matrix in particle-hole (Nambu) space obeying transport-like equations for excitations of energy $`ϵ`$ moving along classical trajectories labelled by the Fermi momentum, $`𝐩_f`$. We use the notation of Ref. Eschrig (2000), set $`\mathrm{}=1,k_B=1`$, and consider spin-independent transport in spin-singlet superconductors.

The basic model for superconducting weak links considered here is that of a constriction of diameter and length on the nanometer scale, much smaller than the coherence length, $`\xi _\mathrm{\Delta }=v_f/\pi \mathrm{\Delta }`$, and the bulk elastic and inelastic mean free paths (see Fig. 1). The potential barrier located at $`z=0`$ is characterized by a transmission (or reflection) probability, $`D(𝐩_f)`$ (or $`R(𝐩_f)=1D(𝐩_f)`$), for normal-state quasiparticles with Fermi momentum $`𝐩_f`$ incident on the interface. The coupling between the two superconductors, $`S_1`$ and $`S_2`$, can then be described by a boundary condition connecting the Green functions for the two superconductors at the junction interface Zaĭtsev (1984). The order parameter at the junction interface for the superconductor $`S_j`$ is $`\mathrm{\Delta }e^{i\varphi _j}`$, and the temperature at the junction interface for superconductor $`S_j`$ is $`T_j`$ for $`j=1,2`$. The phase difference is denoted by $`\varphi =\varphi _2\varphi _1`$, and the temperature bias is $`\delta T=T_2T_1`$.

Recently, Eschrig Eschrig (2000) recast Zaitsev’s boundary condition into a convenient form by parameterizing the quasiclassical Green functions and transport equations using Shelankov’s projection operators Shelankov (1980) and generalized spectral, $`\gamma ^{R,A}`$, and distribution, $`x^K`$, functions obeying Riccatti-type transport equations. We use the Riccatti formulation of the quasiclassical equations with the boundary condition of Ref. Eschrig (2000) to solve for the Keldysh Green’s functions and heat current for superconducting weak links driven out of equilibrium by a temperature bias. The propagators for trajectories incident, $`\widehat{𝔊}_+^{R,A,K}=\widehat{𝔊}_1^{R,A,K}(𝐩_f\widehat{𝐳}>0,z=0^{})`$, and reflected, $`\widehat{𝔊}_{}^{R,A,K}=\widehat{𝔊}_1^{R,A,K}(𝐩_f\widehat{𝐳}<0,z=0^{})`$ by the interface from the $`S_1`$ side can be used to determine the heat current through the interface,

$$I_ϵ=𝒜N_f\frac{dϵ}{4\pi i}ϵv_f\text{Tr}\left(\widehat{𝔊}_+^K(𝐩_f,ϵ)\widehat{𝔊}_{}^K(𝐩_f,ϵ)\right),$$
(1)
where $`N_f`$ is the normal-state density of states at Fermi surface, $`𝐯_f`$ is the Fermi velocity and $`𝒜=\pi a^2`$ is the cross-sectional area of the constriction. The Fermi-surface average includes the direction cosine for projection of the group velocity along the direction normal to the interface; i.e. $`\mathrm{}=\frac{1}{2}_0^{\pi /2}𝑑\theta \mathrm{sin}\theta \mathrm{cos}\theta (\mathrm{})`$, where $`\theta =\mathrm{arccos}(\widehat{𝐯}_f\widehat{𝐳})`$. We consider the case in which $`S_1`$ and $`S_2`$ are identical $`s`$-wave superconductors with isotropic Fermi surfaces; it is straightforward to generalize the results to two different s-wave superconductors. We also consider small junctions, $`a\xi _\mathrm{\Delta }`$; in this limit the Josephson supercurrent through the contact is small by at least a factor $`a/\xi _\mathrm{\Delta }`$ compared to the bulk critical current, so pair-breaking corrections to the order parameter by the supercurrent can be neglected Kulik and Omeĺyanchuk (1978). Thus, to a good approximation the order parameters take their bulk equilibrium values, but with local values for the phase. Also for small constrictions the thermal resistance of the junction is much larger than in that in the bulk, so the temperature drop occurs essentially at the junction.

With these considerations, $`\widehat{𝔊}_\pm ^K`$ can be calculated as follows. First, we express the Green function in terms of Riccati amplitudes Eschrig (2000). For example,

$$\widehat{𝔊}_+^K=\frac{2\pi i}{N_1^RN_1^A}\left(\begin{array}{cc}x_1^K+\stackrel{~}{X}_1^K\gamma _1^R\stackrel{~}{\gamma }_1^A& x_1^K\mathrm{\Gamma }_1^A\stackrel{~}{X}_1^K\gamma _1^R\\ x_1^K\stackrel{~}{\mathrm{\Gamma }}_1^R\stackrel{~}{X}_1^K\stackrel{~}{\gamma }_1^A& \stackrel{~}{X}_1^K+x_1^K\stackrel{~}{\mathrm{\Gamma }}_1^R\mathrm{\Gamma }_1^A\end{array}\right),$$
(2)
where $`N_1^RN_1^A=(1+\gamma _1^R\stackrel{~}{\mathrm{\Gamma }}_1^R)(1+\stackrel{~}{\gamma }_1^A\mathrm{\Gamma }_1^A)`$. The advanced amplitudes are obtained from retarded functions using the symmetry $`\gamma ^A=(\stackrel{~}{\gamma }^R)^{}`$. In the point contact geometry, the amplitudes and distribution functions for incoming quantities (lower case) take their local equilibrium values: $`\gamma _j^R=\stackrel{~}{\gamma }_j^R(ϵ)^{}=i\mathrm{\Delta }e^{i\varphi _j}/(\epsilon ^R+i\sqrt{\mathrm{\Delta }^2(\epsilon ^R)^2})`$, $`x_j^K=\stackrel{~}{x}_j^K(ϵ)^{}=(1|\gamma _j^R|^2)\mathrm{tanh}(ϵ/2T_j)`$, for $`j=1,2`$. Using the boundary conditions of Ref. Eschrig (2000), we construct the corresponding functions for outgoing trajectories (upper case),

$`\stackrel{~}{\mathrm{\Gamma }}_1`$ $`=`$ $`{\displaystyle \frac{R\left(1+\stackrel{~}{\gamma }_2\gamma _2\right)\stackrel{~}{\gamma }_1+D\left(1+\stackrel{~}{\gamma }_1\gamma _2\right)\stackrel{~}{\gamma }_2}{1+R\gamma _2\stackrel{~}{\gamma }_2+D\stackrel{~}{\gamma }_1\gamma _2}},`$ (3)
$`\stackrel{~}{X}_1`$ $`=`$ $`{\displaystyle \frac{R\left|1+\stackrel{~}{\gamma }_2\gamma _2\right|^2\stackrel{~}{x}_1+D\left|1+\stackrel{~}{\gamma }_1\gamma _2\right|^2\stackrel{~}{x}_2RD\left|\stackrel{~}{\gamma }_1\stackrel{~}{\gamma }_2\right|^2x_2}{|1+R\gamma _2\stackrel{~}{\gamma }_2+D\stackrel{~}{\gamma }_1\gamma _2|^2}},`$
where we omitted the superscripts. Inserting these expressions into Eq. (2), and performing the analogous calculation for $`\widehat{𝔊}_{}^K`$, we obtain explicit expressions for the phase-sensitive thermal conductance, defined by $`I_ϵ=\kappa (\varphi ,T)\delta T`$, in the limit $`\delta T0`$. The general result can also be used to calculate the heat current beyond the linear response limit. A more detailed derivation and discussion will be presented elsewhere Zhao et al. (2003).

In the clean limit, $`\epsilon ^Rϵ+i0^+`$, the thermal conductance is expressed in terms of the transmission of bulk excitations of energy $`ϵ\mathrm{\Delta }`$ and group velocity, $`v_g(ϵ)=v_f\sqrt{ϵ^2\mathrm{\Delta }^2}/ϵ`$ through the junction,

$$\kappa (\varphi ,T)=𝒜_\mathrm{\Delta }^{\mathrm{}}𝑑ϵ𝒩(ϵ)\left[ϵv_g(ϵ)\right]𝔇(ϵ,\varphi )\left(\frac{f}{T}\right),$$
(4)
where $`f(ϵ)=(e^{ϵ/T}+1)^1`$ is the Fermi function, $`𝒩(ϵ)=N_fϵ/\sqrt{ϵ^2\mathrm{\Delta }^2}`$ is the bulk density of states (DOS), and $`𝔇(ϵ,\varphi )=𝔇_{\text{ee}}(ϵ,\varphi )+𝔇_{\text{eh}}(ϵ,\varphi )`$ is the transmission coefficient for the heat current, which is the sum of

$$𝔇_{ee}(ϵ,\varphi )=D\frac{(ϵ^2\mathrm{\Delta }^2)(ϵ^2\mathrm{\Delta }^2\mathrm{cos}^2\frac{\varphi }{2})}{\left[ϵ^2\mathrm{\Delta }^2(1D\mathrm{sin}^2\frac{\varphi }{2})\right]^2},$$
(5)
the transmission coefficient for electron-like (hole-like) quasiparticles remaining electron-like (hole-like), and

$$𝔇_{eh}(ϵ,\varphi )=D(1D)\frac{(ϵ^2\mathrm{\Delta }^2)\mathrm{\Delta }^2\mathrm{sin}^2\frac{\varphi }{2}}{\left[ϵ^2\mathrm{\Delta }^2(1D\mathrm{sin}^2\frac{\varphi }{2})\right]^2},$$
(6)
the transmission coefficient for electron-like (hole-like) quasiparticles with branch conversion to hole-like (electron-like) quasiparticles. Here we neglect the angular dependence of the barrier transmission and reflection probabilities 111More realistic models for the barrier transmission which take into account the reduction in the transmission probability for trajectories away from normal incidence do not lead to significant changes in the results for constant $`D`$..

The heat current density carried by bulk quasiparticles of energy $`ϵ`$ in the superconducting leads reduces to the normal-state current density, $`𝒩(ϵ)[ϵv_g(ϵ)]=N_fϵv_f`$; the increase in bulk DOS is compensated by the reduction in the group velocity. For $`\varphi =0`$, $`𝔇(ϵ,\varphi )`$, reduces to the barrier transmission probability for normal-state quasiparticles, $`𝔇(ϵ,0)=D`$. Thus, for $`\varphi =0`$ the thermal conductance of the ScS contact is simply reduced by the opening of the gap in the quasiparticle spectrum. However, for $`\varphi 0`$ the transmission coefficient, $`𝔇(ϵ,\varphi )`$, includes the modification of the local DOS near the contact by the formation of an Andreev bound state (ABS) with energy below the gap edge, as well as the particle-hole coherence amplitudes which alter direct ($`ee`$) transmission and generate branch conversion ($`eh`$) scattering.

The relative importance of the direct ($`ee`$) and branch-conversion ($`eh`$) processes to the phase dependence of the thermal conductance depends on the barrier transparency $`D`$. For both processes the ABS plays a central role in controlling the phase modulation of the conductance. The bound state leads to a reduction in the local DOS near the contact and to a corresponding suppression of the transmission coefficient for excitations with $`ϵ=\mathrm{\Delta }`$. For moderate to high transmission barriers ($`D0.5`$) this leads to suppression of the thermal conductance for $`\varphi \pi `$. For low transmission barriers ($`D1`$) multiple Andreev reflection leads to a shallow bound state just below the continuum edge at $`ϵ_\text{b}=\mathrm{\Delta }\sqrt{1D\mathrm{sin}^2(\frac{\varphi }{2})}`$. The spectral weight of the ABS is derived from the continuum states near $`ϵ=\mathrm{\Delta }`$, which suppresses the divergence at $`ϵ=\mathrm{\Delta }`$ at the cost of a large, but finite, resonant enhancement in the transmission of quasiparticles at energies, $`ϵ\mathrm{\Delta }(1+\frac{\text{1}}{\text{2}}D\mathrm{sin}^2(\frac{\varphi }{2}))`$, above the gap (Fig. 2c). The resonance generates a strong enhancement of the thermal conductance as the phase is tuned to $`\varphi =\pi `$. These features, as well as the evolution of the phase-modulation of the conductance with barrier transmission, are shown in Fig. 2, where we plot the normalized conductance, $`\kappa (\varphi )/\kappa (\varphi =0)`$ for $`0<D1`$ and $`T=0.5\mathrm{\Delta }`$ ($`T=0.72T_c`$). For intermediate values of the barrier transparency, $`D0.5`$, the phase dependence of the conductance is a non-monotonic function of $`\varphi `$ for $`0\varphi \pi `$ (Fig. 2b), although the amplitude of these oscillations is very small. For $`D=1`$, transmission with branch conversion drops out ($`𝔇_{\text{eh}}=0`$) and the transmission coefficient for the quasiparticle heat current reduces to $`𝔇(ϵ,\varphi )=(ϵ^2\mathrm{\Delta }^2)/(ϵ^2\mathrm{\Delta }^2\mathrm{cos}^2(\frac{\varphi }{2}))`$, with a resulting thermal conductance in agreement with Ref. Kulik and Omeĺyanchuk (1992) for a pinhole.

We compare Eq. 4 for $`D1`$ with the heat current obtained by perturbation theory from a tunnelling Hamiltonian (tH) description of SIS tunnel junctions. Based on the tH method Guttman et al. Guttman et al. (1997) obtained a heat current of the form: $`I_0+I_1\mathrm{cos}\varphi `$. If we expand $`𝔇`$ to leading order in the barrier transmission probability, $`D`$, we obtain the tH result for the conductance from the linear response limit of Eq. (2) of Ref. Guttman et al. (1997)b,

$$\kappa ^{\text{tH}}=𝒜N_fv_fD_\mathrm{\Delta }^{\mathrm{}}𝑑ϵϵ\frac{ϵ^2\mathrm{\Delta }^2\mathrm{cos}\varphi }{ϵ^2\mathrm{\Delta }^2}\left(\frac{f}{T}\right).$$
(7)
This result has an unphysical divergence due to the singularity at $`ϵ=\mathrm{\Delta }`$. In the tH method the divergence is regulated by an ad hoc procedure. Guttman et al. Guttman et al. (1997) required a finite temperature difference and $`\mathrm{\Delta }(T_1)\mathrm{\Delta }(T_2)`$ for the gaps of the two superconductors. However, Eqs. 4-6 for arbitrary transparency show that the unphysical divergence is not a singularity of the limit $`\delta T0`$, but a failure of perturbation theory in the tunnel Hamiltonian; which does not include the change in the spectrum near the contact. The bound state and the resonance regulate the singularity obtained in perturbation theory and lead to a thermal conductance that is nonanalytic, $`D\mathrm{ln}D`$, but vanishes for $`D0`$. The result for $`\kappa (\varphi )`$ to order $`D`$ also has non-perturbative corrections to the phase modulation of the conductance, which includes terms $`\mathrm{cos}\varphi `$ as well as $`\mathrm{sin}^2\frac{\varphi }{2}\mathrm{ln}(\mathrm{sin}^2\frac{\varphi }{2})`$,

$$\kappa (\varphi )=\kappa _0\kappa _1\mathrm{sin}^2\frac{\varphi }{2}\mathrm{ln}(\mathrm{sin}^2\frac{\varphi }{2})+\kappa _2\mathrm{sin}^2\frac{\varphi }{2},$$
(8)
where $`\kappa _1=k\text{sech}^2(\mathrm{\Delta }/2T)`$, $`k=𝒜N_fv_fD(\mathrm{\Delta }^3/4T^2)`$, $`\kappa _0=k_1^{\mathrm{}}𝑑xx^2\text{sech}^2(x\mathrm{\Delta }/2T)`$, $`\kappa _2=(1+\mathrm{ln}D)\kappa _1`$ $`+k[(4T/\mathrm{\Delta })(1\mathrm{tanh}(\mathrm{\Delta }/2T))+c]`$, and $`c=2_0^{\mathrm{}}𝑑xx\mathrm{ln}x`$ $`[1+(\mathrm{\Delta }/T)\sqrt{x^2+1}\mathrm{tanh}(\mathrm{\Delta }\sqrt{x^2+1}/2T)]`$ $`(x^2+1)^{3/2}`$ $`\text{sech}^2(\mathrm{\Delta }\sqrt{x^2+1}/2T)`$. The relative magnitude of the non-perturbative correction, $`\kappa _1/\kappa _2`$, is approximately $`25\%`$ for $`D=0.01`$ at $`T/T_c=0.8`$ and increases with decreasing temperature.

For general transparency the magnitude of the phase modulation of the thermal conductance is a maximum for $`\varphi =\pi `$, except for a small range of barriers with $`D1/2`$. The temperature dependence of the conductance for $`\varphi =\pi `$ is plotted in Fig. 3. The thermal conductance for $`\varphi =0`$, is also shown for comparison. For moderate to high-transmission junctions ($`D1/2`$) the thermal conductance for $`\varphi 0`$ is suppressed relative to the conductance at $`\varphi =0`$ at all temperatures. However, for low-transparency junctions ($`D1`$) resonant transmission of quasiparticles just above the gap edge leads to *increase* in the conductance when $`T`$ drops below $`T_c`$. This effect is pronounced for junctions with $`D0.2`$; its observation would provide a test of this theory of phase-induced resonant transmission of quasiparticles.

The results above were obtained in the clean limit for the superconducting leads. In the diffusive limit, $`k_f^1\mathrm{}\xi _0`$, where $`\mathrm{}`$ is the elastic mean-free path, the excitations and pairing correlations are governed by Usadel’s diffusion equations Usadel (1970) for the Fermi-surface averaged propagators, $`\widehat{𝔤}_j^{\text{A,R,K}}=d^2𝐩_f\widehat{𝔊}_j^{\text{A,R,K}}(ϵ,𝐩_f;𝐑)`$. For an ScS contact Nazarov derived a boundary condition for the propagator in diffusive conductors Nazarov (1999),

$$\sigma _2\stackrel{ˇ}{𝔤}_z\stackrel{ˇ}{𝔤}|_2=\frac{1}{𝒜R_\text{b}}\frac{2D[\stackrel{ˇ}{𝔤}_2,\stackrel{ˇ}{𝔤}_1]}{4+D\left(\{\stackrel{ˇ}{𝔤}_2,\stackrel{ˇ}{𝔤}_1\}2\right)}_D,$$
(9)
where $`\stackrel{ˇ}{𝔤}_j`$ is the Keldysh matrix representation for the $`\widehat{𝔤}_j^{\text{A,R,K}}`$, $`R_\text{b}`$ is the barrier resistance for normal leads and $`\mathrm{}_D=𝑑D\rho (D)\mathrm{}/𝑑D\rho (D)D`$ is an average over a distribution of channels with transmission coefficient $`D`$ characterizing the interface. For a single channel contact with transmission coefficient $`D`$ application of Eq. 9 yields the result from Eqs. 4-6 obtained in the ballistic limit with the replacement: $`N_fv_f𝒜D/41/2e^2R_\text{b}`$. Thus, the phase modulation of the thermal conductance of small Josephson weak links are the same in the clean and diffusive limits. This result is due to the cancellation of impurity renormalization of the diagonal and off-diagonal self-energies in the propagators for s-wave superconductors up to order $`a/\xi _\mathrm{\Delta }`$, and that Nazarov’s boundary condition is based on a junction model with a central layer and interface described by Zaitsev’s boundary condition.

In summary, we have presented a theory for heat transport through Josephson weak links. For high transmission junctions the reduction in states with $`ϵ\mathrm{\Delta }`$, resulting from the formation of an ABS near the Fermi level, leads to a suppression of the conductance near $`\varphi =\pi `$. For small transparency, the presence of a shallow bound state produces a resonance in the continuum just above the gap edge. This leads to an increase in conductance as the temperature drops below $`T_c`$ for junctions with $`\varphi \pi `$. For a single channel contact, these results are insensitive to impurity scattering and hold in the clean and dirty limits.

This work was supported by the NSF grant DMR 9972087, and STINT, the Swedish Foundation for International Cooperation in Research and Higher Education.


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# References

AN ESTIMATE OF THE PERCOLATION PARAMETER IN HEAVY ION COLLISIONS

J.Dias de Deus and Yu. M. Shabelski
CENTRA, Instituto Superior Técnico, 1049-001 Lisboa, Portugal

ABSTRACT

From existing hadron and heavy ion collisions data on $`\overline{p}/p`$ central production we estimate the value of the percolation parameter at RHIC energies.

Permanent address: Petersburg Nuclear Physics Institute, Gatchina, St.Petersburg, Russia
E-mail: shabelsk@thd.pnpi.spb.ru

It is well-known that in high energy hadron-nucleus collision there exists inelastic screening  experimentally confirmed, especially for the case of hadron-deuteron interactions. The same inelastic screening has to exist in high energy heavy ion collision, as well. This effect is very small for integrated cross sections (because many of them are determined by geometry), but it is very important  for the calculations of secondary multiplicities and inclusive densities. Similar results are obtained  in the framework of string fusion , or percolation  models, where string fusion/percolation effects directly correspond  to pomeron interactions and are responsible for the suppression of particle production.

The effect of percolation for central heavy ion collision is, in good approximation determined by the reduction factor

$$F(\eta )=\sqrt{\frac{1\mathrm{exp}^\eta }{\eta }},$$
(1)
$`\eta `$ being the transverse density parameter,

$$\eta =\frac{r_s^2N_s}{R^2},$$
(2)
where $`r_s`$ is the string transverse radius (phenomenological estimation gives $`r_s0.20.3fm`$ ), $`R^2`$ the square of nuclear overlapping which for central collisions is equal to nuclear radius squared and $`N_s`$ is the number of produced strings. At $`\eta 0,F(\eta )1`$ (no percolation/inelastic screening) and at $`\eta \mathrm{},F(\eta )1/\sqrt{\eta }`$ (maximal screening). The detailed discussion of these behaviours can be found in .

In the present paper we will give an estimate for the percolation parameter $`\eta `$ from experimental data, not all of them connected to heavy ion physics.

Let us, in fact, start from $`\gamma p`$ collisions at $`W200`$ GeV (HERA). In lab. frame the asymmetry between comparatively slow $`p`$ and $`\overline{p}`$ was observed to be

$$A_B=2\frac{N_pN_{\overline{p}}}{N_p+N_{\overline{p}}}=(8.0\pm 1.0\pm 2.5)\%.$$
(3)
That corresponds to the yield ratio

$$R^{\gamma p}=N_{\overline{p}}/N_p=0.92\pm 0.03.$$
(4)
However, the HERA kinematics is an asymmetrical one and particles rather slow in lab. HERA frame are rather fast in c.m. frame. To account for this we can use the Quark-Gluon String Model (QGSM)  with string junction diffusion, see details in . This correction is not numerically large, the model estimation for c.m. photon-proton frame gives $`R^{\gamma p}=0.86\pm 0.02`$.

In $`\gamma p`$ collisions we have the baryon number flux from one proton. In the case of $`pp`$ interactions this flux should be two times larger, that corresponding to

$$R^{pp}=0.720.76$$
(5)
in c.m. $`pp`$ frame.

The ratio $`R^{AuAu}`$ in central region of $`AuAu`$ collisions was measured at energy 200GeV per nucleon at RHIC. The values are $`0.74\pm 0.02\pm 0.03`$  and $`0.75\pm 0.04`$ , i.e. practically the same as we obtain for $`pp`$ collisions. This is in principle unexpected as the sea contribution, which is $`\overline{p}p`$ symmetrical, is much more important in heavy ion collisions. The string fusion/screening argument gives a fair explanation of what happens.

Now let us note that in the QGSM as well as in the Dual String Model (DSM)  the multiplicity of every secondary $`h`$ produced in $`pp`$ collision can be written as

$$<n_h^{pp}>=V_h+S_h,$$
(6)
where $`V_h`$ and $`S_h`$ are the contributions of valence and sea quarks, respectively.

In the case of heavy ion collisions the correspondent equation can be written as

$$<n_h^{AA}>=N_{pair}V_h+(<\nu >_{AA}N_{pair})F(\eta )S_h,$$
(7)
where $`N_{pair}`$ is the number of pair of nucleon-nucleon interactions and $`<\nu >_{AA}`$ is the total number of binary interactions. $`F(\eta )`$ accounts for the sea strings percolation effect, a negligible effect for $`pp`$ collisions.

The structure of this Eq. is rather evident, for equal nuclei we have $`N_{pair}`$ interactions of valence quarks and diquarks (valence-valence strings) and all another $`<\nu >_{AA}N_{pair}`$ are sea quark interactions (sea-sea strings) by definitions. Of course it is true only in average, in every separate event the situation can be more complicated because the number of interacting nucleons in every nucleus can be different.

We account the percolation factor in Eq.(7) only for sea string contribution due to three reasons. First of all, the number of sea strings is in our case about 5 times larger than the number of valence strings, so percolation effects for sea strings are more important. Second and more physically important reason is that valence-valence strings (contribution $`V_h`$ in Eq. (7)) are long in rapidity space whereas sea-sea strings are rather short and their ends are distributed more close to the central region. The suppression for the inelastic screening effects coming from nuclei form factors (see  for details) allows the total fusion of sea-sea strings but valence-valence strings can be fused only in part, so the fusion/percolation effects will be important for the last ones only at very high energies. Third, more model dependent reason is that in DTU approach the interacting of valence quarks is considered as a first step, and after several sea quark interactions can be added, if necessary. So, the screening effects should decrease firstly the number of sea-sea strings.

In order to have $`R^{pp}/R^{AA}1`$ at RHIC energies, as experimentally observed, the ratio between valence quark and sea quark contributions in Eqs. (6) and (7) should be approximately the same. So we have

$$\frac{(<\nu >_{AA}N_{pair})F(\eta )}{N_{pair}}1.$$
(8)
Using the experimental estimates of $`<\nu >_{AA}`$ and $`N_{pair}`$ from  for high-$`p_T`$ hadron production (these values are in agreement with standard Glauber-like estimates ) we obtain for the most central collisions the value $`F(\eta )=1/4.8`$, giving

$$\eta =23.$$
(9)
Due to experimental errors and some model calculations we estimate the error bar in the last value to be a factor of the order 1.5. This result agrees with an estimate of $`\eta `$, making use of $`pp`$ central charged particle densities at $`\sqrt{s}`$ 200 GeV, $`\eta 16`$ (see ). The value obtained for $`\eta `$ shows that we are well inside the percolation (perhaps quark-gluon plasma) region. Note that if $`R^{pp}>R^{AA}`$, as it would have happened without the centre of mass correction bringing $`R^{\gamma p}`$ down, from = 0.92 to 0.86, then the $`\eta `$ value should have been even larger.

The contributions of valence and sea strings in QGSM for $`pp`$ collisions are of the same order. For $`AuAu`$ central interaction the sea contribution is enhanced by the factor

$$\frac{<\nu >_{AA}N_{pair}}{N_{pair}},$$
(10)
which is, without percolations, about 4.8. That should increase the inclusive density of secondaries. The suppression factor $`F(\eta )`$ about 1/5 for sea contribution decreases the total rapidity density in central region about 2.5 or 3 times, that is in agreement with the previous calculations of refs. .

In our approach, the reason why the ratio $`\overline{p}p`$ is not much larger in heavy ion collisions is caused by the same mechanism that limits particle density in central rapidity: string fusion. It would be interesting to see if saturation models  can also obtain a similar effect in $`\overline{p}p`$ suppression.

We are grateful to N.Armesto for discussions.