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# Flexoelectricity and piezoelectricity - reason for rich variety of phases in antiferroelectric liquid crystals

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## Abstract

The free energy of antiferroelectric liquid crystal which takes into account polar order explicitly is presented. Steric, van der Waals, piezoelectric and flexoelectric interactions to the nearest layers and dipolar electrostatic interactions to the nearest and to the next nearest layers induce indirect tilt interactions with chiral and achiral properties, which extend to the third and to the fourth nearest layers. Chiral indirect interactions between tilts can be large and induce helicoidal modulations even in systems with negligible chiral van der Waals interactions. If indirect chiral interactions compete with chiral van der Waals interactions, the helix unwinding is possible. Although strength of microscopic interactions change monotonically with decreasing temperature, effective interlayer interactions change nonmonotonically and give rise to nonmonotouous change of modulation period through various phases. Increased enatiomeric excess i.e. increased chirality changes the phase sequence.

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Chiral polar smectics are materials which form layered phases. In these phases the average direction of elongated molecules is tilted for an angle with respect to the layer normal. Smectic layers are spontaneously polarized in the plane of the layer and perpendicular to the direction of the tilt . Among these polar smectics the most widely experimentally and theoretically studied materials are ferroelectric liquid crystals. Ten years ago at an attempt to synthesise ferroelectric liquid crystals with larger polarization, antiferroelectric liquid crystals were discovered . Their synthesis stimulated extensive experimental research which resulted in a discovery of many new polar liquid crystalline phases. In addition to the the ferroelectric Sm C phase and the antiferroelectric Sm C$`{}_{A}{}^{}{}_{}{}^{}`$ phase, the Sm C$`{}_{\alpha }{}^{}{}_{}{}^{}`$ phase and the Sm C$`{}_{\gamma }{}^{}{}_{}{}^{}`$ phase were found to exist in some materials while in others instead of the Sm C$`{}_{\gamma }{}^{}{}_{}{}^{}`$ phase, two phases - the Sm C$`{}_{FI2}{}^{}{}_{}{}^{}`$ phase and the Sm C$`{}_{FI1}{}^{}{}_{}{}^{}`$ phase are present. The phases are modulated along layer normal and the modulation period of these phases was determined by resonant X-ray scattering . The period was shown to vary nonmonotonically with decreasing temperature from a few layers in the Sm C$`{}_{\alpha }{}^{}{}_{}{}^{}`$ phase, to a few hundred layers in the Sm C phase, to approximately four layers in the Sm C$`{}_{FI2}{}^{}{}_{}{}^{}`$ phase, to approximately three layers in the Sm C$`{}_{FI1}{}^{}{}_{}{}^{}`$ phase and to approximately two layers in the Sm C$`{}_{A}{}^{}{}_{}{}^{}`$ phase at low temperatures.

Antiferroelectric liquid crystals can be theoretically described by continuous models  that predict only two of experimentally observed phases, the ferroelectric Sm C phase and the antiferroelectric Sm C$`{}_{A}{}^{}{}_{}{}^{}`$ phase. Discrete models  take interlayer interactions between the tilt vectors explicitly into account. The model  considers competing interactions between tilts in nearest layers and in next nearest layers and predicts various structures where the direction of the tilt varies uniformly from layer to layer. The model was later called the clock model .

Within this model the observed nonmonotonous temperature dependence of the modulation period can be reproduced only with nonmonotonous temperature dependences of model parameters, which cannot be understood from microscopic interactions. Although the model can predict structures of the Sm C$`{}_{FI2}{}^{}{}_{}{}^{}`$ and of the Sm C$`{}_{FI1}{}^{}{}_{}{}^{}`$ for the specific set of clock model parameters, these phases cannot exist as stable phases in a broader temperature interval. For this some synclinic interactions would be needed between the third and between the fourth nearest layers .

In this letter we present the model where the polarization of smectic layers is taken explicitly into account and is treated as a secondary order parameter to the tilt. In addition to the steric and van der Waals interactions to the nearest layers between the tilt vectors we consider also piezoelectric and flexoelectric couplings between the tilt and the polarization and electrostatic interactions between the polarizations of the nearest layers and polarizations with the next nearest layers .

To describe the structure of phases, we introduce the tilt vector $`𝝃_j`$ which gives the magnitude and the direction of the tilt in the $`j`$-th smectic layer and the polar order parameter $`𝜼_𝒋=\{\eta _{jx},\eta _{jy}\}`$ which gives the magnitude and the direction of the in plane transverse polar order in the $`j`$-th layer. The spontaneous polarization in the j-th layer is proportional to the polar order $`𝜼`$: $`P_j=P_0𝜼_j`$, where $`P_0`$ is a layer polarization for a completely polarly ordered layer . Therefore polar order parameter $`𝜼`$ will be here shortly called polarization. The free energy of the smectic system with N layers can be expressed in terms of both order parameters as:

$`\stackrel{~}{G}`$ $`=`$ $`{\displaystyle \underset{j=1}{\overset{N}{}}}{\displaystyle \frac{1}{a}}G_0+{\displaystyle \frac{1}{2}}a_1\left(𝝃_j𝝃_{j+1}\right)+{\displaystyle \frac{1}{2}}f_1\left(𝝃_j\times 𝝃_{j+1}\right)_z+`$ (1)
$`+`$ $`{\displaystyle \frac{1}{2}}b_0𝜼_j^2+{\displaystyle \frac{1}{2}}b_1\left(𝜼_j𝜼_{j+1}\right)+{\displaystyle \frac{1}{8}}b_2\left(𝜼_j𝜼_{j+2}\right)+`$ (2)
$`+`$ $`c_p\left(𝜼_j\times 𝝃_j\right)_z+{\displaystyle \frac{1}{2}}\mu \left(𝝃_{j+1}𝝃_{j1}\right)𝜼_j.`$ (3)
Here $`G_0=1/2a(TT_0)\xi _j^2+1/4b\xi _j^4`$ is the tilt dependent free energy of an isolated layer, where a continuous transition to the tilted phase takes place at $`T_0`$. Dividing all terms by the parameter $`a`$, we express all model parameters as well as the free energy $`\stackrel{~}{G}`$ in the units of temperature. Parameter $`a_1`$ corresponds to steric and van der Waals interactions between nearest layers. Steric interactions favor synclinic molecular alignment in neighboring layers and give a negative contribution to $`a_1`$, while van der Waals intermolecular interactions favor anticlinic ordering in neighboring layers and give a positive contribution to $`a_1`$. The parameter $`a_1`$ is of the order of a few Kelvins . We believe that steric and van der Waals interactions are negligible further than to the nearest layers. The parameter $`f_1`$ gives the chiral part of van der Waals interactions between molecules in neighboring layers and vanishes in racemic mixtures. We assume that $`f_1`$ is smaller than $`a_1`$ and it is a few tenths of a Kelvin. Polar vectors are associated with the layer polarization via magnitude and direction of molecular dipole moments. The parameter $`b_0`$ is positive because polarization is not a proper order parameter and both $`b_1`$ and $`b_2`$ favor antiparallel dipolar order and are therefore positive . Since they give intralayer and interlayer interactions which decrease for more distant layers we expect that $`b_0>>b_1>>b_2`$. Transition temperatures from the Sm C phase to the Sm C$`{}_{A}{}^{}{}_{}{}^{}`$ phase are few degrees lower in nonpolar racemic mixtures than in pure samples  which suggests that $`b_0`$ is also of the order of a few K. Polarization is induced in chiral polar smectics by the tilt and the piezoelectric coupling is given by $`c_p`$. The parameter $`c_p`$ has also a chiral character and vanishes in racemic mixtures. The magnitude of the layer polarization is only one tenth of the polarization of completely polarly ordered system  i.e. the magnitude of $`𝜼_j`$ is of the order 0.1 which means that also the value of $`c_p`$ is of the order of a Kelvin. The polarization coupling with the tilt in neighboring layers is given by $`\mu `$ and is of the same order as $`c_p`$ .

The polar part of the free energy Eq. (3), can be written in the form

$$G_P=𝜼\underset{¯}{C}𝝃+\frac{1}{2}𝜼\underset{¯}{B}𝜼.$$
(4)
The tilt vector is $`2N`$-dimensional vector of the form $`𝝃=\{\xi _{1x},\mathrm{}\xi _{jx},\mathrm{}\xi _{Nx},\xi _{1y,}\mathrm{}\xi _{Ny}\}`$ and similar for the polarization $`𝜼`$. The five-diagonal $`2N`$-dimensional matrix $`\underset{¯}{B}`$ gives intralayer and interlayer electrostatic interactions with elements $`B_{j,j}=b_0,B_{j,j\pm 1}=\frac{1}{2}b_1`$ and $`B_{j,j\pm 2}=\frac{1}{8}b_2`$. The $`2N`$-dimensional matrix $`\underset{¯}{C}`$ gives the coupling between tilts and polarizations. The offdiagonal elements $`C_{j,j\pm 1}=C_{j+N,j+N\pm 1}=\frac{1}{2}\mu `$ and $`C_{j,j+N}=C_{j+N,j}=c_p`$. Minimization of Eq. (4) with respect to polarization $`𝜼`$ gives

$$𝜼=\underset{¯}{B}^1\underset{¯}{C}𝝃,$$
(5)
where $`\underset{¯}{B}^1`$ is the inverse matrix of the five-diagonal matrix $`\underset{¯}{B}`$. As $`b_0>>b_1>>b_2`$ we keep in $`\underset{¯}{B}^1`$ only the terms up to the second order in $`b_1/b_0`$ and up to the first order in $`b_2/b_0`$. The elements of $`\underset{¯}{B}^1`$ are $`B_{j,j}^1=\frac{1}{b_0}\left(1+\frac{1}{2}\left(\frac{b_1}{b_0}\right)^2\right),B_{j,j\pm 1}^1=\frac{1}{2b_0}\left(\frac{b_1}{b_0}\right)`$ and $`B_{j,j\pm 2}^1=\frac{1}{8b_0}\left(2\left(\frac{b_1}{b_0}\right)^2\left(\frac{b_2}{b_0}\right)\right)`$. Inserting the tilt dependent polarization Eq. (5) into Eq. (4) we obtain the polar part of free energy as

$$G_P=\frac{1}{2}𝝃\underset{¯}{C}\underset{¯}{B}^1\underset{¯}{C}𝝃$$
(6)
and the free energy due to interlayer interactions is

$$\stackrel{~}{G}_{\text{int}}=\frac{1}{2}\underset{j=1}{\overset{N}{}}\left(\underset{k=1}{\overset{4}{}}\stackrel{~}{a}_k\left(\xi _j\xi _{j+k}\right)+\underset{k=1}{\overset{3}{}}\stackrel{~}{f}_k\left(\xi _j\times \xi _{j+k}\right)\right).$$
(7)
Parameters $`\stackrel{~}{a}_k`$ and $`\stackrel{~}{f}_k`$ which appear after polarization elimination, give effective interactions between tilts. Although direct van der Waals and steric interactions are significant only to the nearest layers and electrostatic interactions are significant up to the next nearest layers, effective interactions are significant up to the fourth nearest layers.

$`\stackrel{~}{a}_1`$ $`=`$ $`a_1+\left({\displaystyle \frac{c_p^2}{b_0}}+{\displaystyle \frac{1}{4}}{\displaystyle \frac{\mu ^2}{b_0}}\right)\left({\displaystyle \frac{b_1}{b_0}}\right)`$ (8)
$`\stackrel{~}{a}_2`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \frac{c_p^2}{b_0}}\left({\displaystyle \frac{1}{2}}\left({\displaystyle \frac{b_2}{b_0}}\right)\left({\displaystyle \frac{b_1}{b_0}}\right)^2\right)+{\displaystyle \frac{1}{2}}{\displaystyle \frac{\mu ^2}{b_0}}\left(1+{\displaystyle \frac{1}{4}}\left({\displaystyle \frac{b_2}{b_0}}\right)\right)`$ (9)
$`\stackrel{~}{a}_3`$ $`=`$ $`{\displaystyle \frac{1}{4}}{\displaystyle \frac{\mu ^2}{b_0}}\left({\displaystyle \frac{b_1}{b_0}}\right)`$ (10)
$`\stackrel{~}{a}_4`$ $`=`$ $`{\displaystyle \frac{1}{8}}{\displaystyle \frac{\mu ^2}{b_0}}\left(\left({\displaystyle \frac{b_1}{b_0}}\right)^2{\displaystyle \frac{1}{2}}\left({\displaystyle \frac{b_2}{b_0}}\right)\right)`$ (11)
$`\stackrel{~}{f}_1`$ $`=`$ $`f_1{\displaystyle \frac{2c_p\mu }{b_0}}\left(1+{\displaystyle \frac{1}{4}}\left({\displaystyle \frac{b_1}{b_0}}\right)^2+{\displaystyle \frac{1}{8}}\left({\displaystyle \frac{b_2}{b_0}}\right)\right)`$ (12)
$`\stackrel{~}{f}_2`$ $`=`$ $`{\displaystyle \frac{c_p\mu }{b_0}}\left({\displaystyle \frac{b_1}{b_0}}\right)`$ (13)
$`\stackrel{~}{f}_3`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \frac{c_p\mu }{b_0}}\left(\left({\displaystyle \frac{b_1}{b_0}}\right)^2+{\displaystyle \frac{1}{2}}\left({\displaystyle \frac{b_2}{b_0}}\right)\right).`$ (14)
Achiral effective interactions between nearest layers $`\stackrel{~}{a}_1`$ consist of direct steric and van der Waals interactions ($`a_1`$) as well as of indirect interactions due to piezoelectrically and flexoelectrically induced polarization. Achiral interaction between next nearest layers are only indirect and can be for systems with negligible flexoelectric interaction ($`\mu 0`$) either competing  ($`\stackrel{~}{a}_2>0`$) or noncompeting with ($`\stackrel{~}{a}_2<0`$). The second case leads to the validity of the continuous bilayer models , although it seems that the present experimental knowledge supports this possibility by a single experimental evidence . In systems with large flexoelectric interactions ($`|c_p|\frac{b_1}{b_0}<|\mu |`$), $`\stackrel{~}{a}_2`$ is always positive and competes with interactions between nearest layers $`\stackrel{~}{a}_1`$. Indirect effective interactions between third neighbors are given by $`\stackrel{~}{a}_3`$. The term is always negative and favors synclinic tilt directions in interacting layers. Therefore this term in systems with significant flexoelectric interactions tends to stabilize the structures with three layer periodicity. Indirect effective interactions between fourth nearest layers $`\stackrel{~}{a}_4`$ can be either negative or positive.

The effective chiral coupling between neighboring layers has two contributions: the van der Waals originated ($`f_1`$) and the polarization part which appears due to the combination of piezo and flexoelectricity ($`c_p\mu /b_0`$). Even systems with negligible direct chiral interactions $`f_10`$ are hellicoidally modulated. In all previous models, chiral interactions have always been treated as weak interactions which induce only slight perturbations in the structure i.e. helicoidal modulations with very long periods. In antiferroelectric liquid crystals this is not always the case. The ratio $`c_p\mu /b_0`$ can have the value of a few Kelvins and is comparable to other achiral interlayer interactions. The competition between the van der Waals part of chiral interactions ($`f_1`$) and indirect chiral interactions due to piezoelectric and flexoelectric effect ($`c_p\mu /b_0`$) can explain the helix unwinding without polarization reversal as observed in the antiferroelectric phase of various systems .

The simplest solution, which minimizes the free energy Eq. (6) for competing interlayer interactions ($`\stackrel{~}{a}_2>0`$), is the clock model solution with the constant phase difference between neighboring layers over the whole sample . The tilt in the j-th layer is $`\xi _j=\theta \{\mathrm{cos}(j\alpha ),\mathrm{sin}(j\alpha )\}`$ where $`\theta `$ is constant and the phase difference $`\alpha `$ is the difference in directions of the tilt vectors in neighboring layers. The phase difference $`\alpha `$ is obtained by the minimization of the free energy Eq. (6) with respect to $`\alpha `$.

We have analyzed the temperature dependence of solutions for the following behavior of model parameters with decreasing temperature: $`a_1`$ increases monotonically from the negative value to the positive value, piezoelectric parameter $`c_p`$ monotonically increases and flexoelectric parameter $`\mu `$ monotonically decreases. Let us consider a microscopic mechanism of the described parameter dependence with decreasing temperature. The monotonous increase of direct interactions $`a_1`$ with decreasing temperature from negative value which is due to interpenetrating molecules through nearest layers, to the positive value in the region where van der Waals interactions favor anticlinic order, is due to increasing smectic order . The flexoelectric coupling ($`\mu `$) decreases monotonically with decreasing temperature, since the smectic order and hindrance of the rotation becomes less affected by the molecules above and below the interacting layer. In contrast, with decreasing temperature piezoelectric coupling ($`c_p`$) monotonically increases since higher smectic order strengthen the rotation hindrance within the layer.

For positive $`\stackrel{~}{a}_2`$ we can introduce the measure of the competition - the competition ratio $`4\stackrel{~}{a}_1/\stackrel{~}{a}_2`$. In racemic mixtures in the temperature region where the competition ratio is smaller than -1, the synclinic nonmodulated Sm C phase is stable. In the temperature region where the competition ratio is larger than 1, the anticlinic nonmodulated Sm C$`{}_{A}{}^{}{}_{}{}^{}`$ phase exists. In the region in between, the phase angle $`\alpha `$ changes with decreasing temperature rapidly from $`0^{}`$ to $`180^{}`$ i.e. modulation period changes from infinity to two layers. In slightly chiral systems the Sm C$`{}_{\alpha }{}^{}{}_{}{}^{}`$ phase appears above the ferroelectric Sm C phase. With additional increase of the enantiomeric excess or increased chirality of the system (larger $`c_p`$), the ferroelectric Sm C phase dissapear, leaving only modulated phase with short pitch (Fig. 1).

Experimental observations have shown that in racemic mixtures only the synclinic Sm C phase and the anticlinic Sm C$`{}_{A}{}^{}{}_{}{}^{}`$ phase exist with the first order transition between them . The narrow temperature range of the modulated phase (Fig. 1 - solid line), can be experimentally seen as the first order transition. In chiral samples two additional phases the Sm C$`{}_{\alpha }{}^{}{}_{}{}^{}`$ phase and the Sm C$`{}_{\gamma }{}^{}{}_{}{}^{}`$ phase appear. In chiral systems where piezoelectric coupling $`c_p`$ is important, below the transitions temperature to the tilted phase, the modulation period is much shorter and increases with decreasing temperature. The temperature region where competition ratio is between -1 and +1 becomes wider and can be experimentally observed as a distinguished Sm C$`{}_{\gamma }{}^{}{}_{}{}^{}`$ phase. The similar behavior is observed in chiral samples of MHPOBC and 10OTBBB1M7  (Fig. 1 - dashed line). If piezoelectric $`c_p`$ coupling is still stronger, the ferroelectric Sm C phase dissapears, which was observed in some systems (Fig. 1 - dotted line). The present form of the model takes into account only quadratic interactions and can not account for first order transitions between phases with different values of $`\alpha `$.

The symmetry of structures with various $`\alpha `$ is the same, since the symmetry operation common to all structures consists from the translation for a layer thickness and the rotation for an angle $`\alpha `$. If $`\alpha `$ changes discontinuously, the temperature range of different phases can be defined with DSC or similar measurements. If transitions are continuous, the temperature ranges of various phases are defined by changes of the macroscopic properties and are to some extent arbitrary. The phase difference $`\alpha `$ can be used as a parameter which distinguishes between different phases. In the Sm C$`{}_{\alpha }{}^{}{}_{}{}^{}`$ phase varies from $`\alpha 10^{}`$ to $`70^{}`$ which means that the modulation period varies from 40 to 5 layers. In the Sm C phase is $`\alpha 0`$ i.e. the infinite modulation period in racemic mixtures and a few hundred layers in pure samples. In the Sm C$`{}_{FI2}{}^{}{}_{}{}^{}`$ phase is $`\alpha 90^{}`$ or four layers, in the Sm C$`{}_{FI1}{}^{}{}_{}{}^{}`$ phase is $`\alpha 120^{}`$ or three layers. In the Sm C$`{}_{A}{}^{}{}_{}{}^{}`$ phase is $`\alpha 180^{}`$. The modulation period is two layers and can also be analyzed within a bilayer model  where it is treated as a long double helix.

To conclude, we present the phenomenological model based on microscopic intralayer and interlayer interactions. Polarization is induced by piezoelectric and flexoelectric effect and is taken into account explicitly. Although tilts directly interact only with nearest layers and polarizations interact up to the next nearest layers, indirect achiral interactions which tend to stabilize structures with three layer and four layer periodicities extend to the fourth neighboring layers. Chiral piezoelectric couplings influence also the effective achiral interactions between nearest layers. Additionally, chiral interactions due to the flexoelectric effect are important to the third nearest layers and can be strong. Direct interactions between nearest layers correspond to elastic terms in continuous models. As a consequence of the piezoelectric and flexoelectric coupling, the corresponding Lifshitz parameter in continuous models is renormalized. In contrast, variation of polarization, which is considered as electrostatic interlayer coupling, has no corresponding terms in continuous models. The large variety of phases in antiferroelectric liquid crystals is a consequence of a delicate balance between various mechanisms. In chiral samples all interactions change with temperature monotonically. But the competition ratio varies nonmonotonically and therefore also phase difference $`\alpha `$ i.e. modulation period changes nonmonotonically and the ferroelectric Sm C phase with long modulation period can be stable between two phases (Sm C$`{}_{\alpha }{}^{}{}_{}{}^{}`$ and Sm C$`{}_{FI2}{}^{}{}_{}{}^{}`$ ) with much shorter modulation periods.

Within the phenomenological discrete model we studied only the simplest possible interlayer interactions and the simplest possible clock model solutions. As a future problem we left the analysis of the influence of the phase difference $`\alpha `$ on the tilt which could induce first order transitions between phases. We also did not consider quadrupolar coupling, which could induce quadrupolar ordering and therefore allow for distorted clock model solutions .

Authors are very grateful to Ewa Gorecka and Nataša Vaupotič for many stimulating discussions. The financial support of Ministry of Education, Science and Sport of Slovenia, grant PO-518 is acknowledged.


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# Partition functions and symmetric polynomials

## 1 Introduction

The theory of ideal quantum gases, although a standard section in every modern textbook on statistical mechanics, is far from being a closed field of research. On one hand, there are continuous attempts towards a deeper understanding of the foundations of the field and to disclose unexpected regularities and relations between known facts. As examples we quote the work of M. H. Lee  on a unified treatment of Fermi and Bose gases and our earlier paper on a fermion-boson symmetry for harmonic oscillators of odd space dimensions . Also this article is intended to contribute to such foundational questions

On the other hand, there are various applications of the theory of ideal gases in almost all areas of modern physics, despite the apparent over-simplification of non-interacting particles. In nuclear physics the shell model is a prominent representative, which at low excitation energies describes the motion of noninteracting fermions in a common (mean) field . In solid state physics of one space dimension interacting fermions may be described as noninteracting bose gases (Luttinger liquids) . The crucial point is that the specific heat of $`N`$ fermions and bosons is the same for equidistant energy spectra, for recents works see .

In atomic physics the concept of ideal quantum gases helped to understand experiments on magnetically trapped atomic vapours . Here the system can be well described as an ideal quantum gas contained in an external harmonic oscillator potential, for an overview see . Also the case of constant and small particle number $`N`$ turns out to be of interest, thereby excluding the use of a grand canonical ensemble ($`N`$ fluctuating) and/or the thermodynamic limit ($`N\mathrm{}`$). Examples of applications, except the above-mentioned trapped systems, are quantum dots  and fluorescence from a few electrons . For a comparison of canonical and grand canonical results in a two-state system see also .

In the context of these small quantum systems it is sometimes of interest to explicitely calculate the $`N`$particle partition function $`Z_N^\pm `$, where $`+`$ stands for bosons and $``$ for fermions. For this purpose a certain recurrence relation for $`Z_N^\pm `$ has recently been used by several authors . It seems that none of the authors, including us, was aware that this recurrence relation could be traced back to the time-honoured textbook of P. Landsberg . Even more remarkable we find that, in some sense, Landsberg’s formula was already discovered by Isaac Newton. Of course, Newton did not know anything about partition functions and Fermi/Bose statistics. However, there is an intimate connection between partition functions and symmetric polynomials, which allows to translate certain theorems on symmetric functions into statements about physical partition functions and vice versa. This will be the main subject of the present article.

The basic idea will be spelled out in section 2. Since we write this article for people who may be experts in either field, combinatorics and statistical mechanics, but not in both, we will give some rather elementary introductions into the field of symmetric polynomials (section 3) and partition functions (section 4). Section 4 also contains the “dictionary” needed for the translation between statements of the respective fields. Thus we obtain the following results, which now appear obvious, but have not yet been explicitely mentioned in the physics literature, namely that $`Z_N^+`$ may be expressed by the $`Z_n^{},nN`$ and vice versa. The most compact expression of this is the statement that the grand canonical partition functions satisfy $`𝒵^+(z)𝒵^{}(z)=1`$. In section 5 we add some closing remarks.

## 2 The basic idea

Before going into details we will describe the basic idea of the correspondence between partition functions and symmetric polynomials and illustrate this idea for the simple example of a system with $`L=3`$ energy levels and $`N=2`$ particles.

It is well-known that the eigenstates of the $`N`$particle Hamiltonian $`H_N^\pm `$ ($`+`$ for bosons, $``$ for fermions) of $`N`$ non-interacting particles can be labelled by occupation number sequences $`(n_1,n_2,\mathrm{},n_L)`$, where $`_{\mathrm{}=1}^Ln_{\mathrm{}}=N`$ and $`n_{\mathrm{}}=0,1`$ for fermions. The latter condition expresses the Pauli principle. Equivalently, the eigenstates are in $`1:1`$-correspondence to the monomials $`x_1^{n_1}x_2^{n_2}\mathrm{}x_L^{n_L}`$ of degree $`N`$, where the $`x_1,x_2,\mathrm{},x_L`$ are (symbolic) commuting variables. In our example, we obtain the monomials $`x_1x_2,x_1x_3,x_2x_3`$ for the fermionic case, and, additionally, $`x_1^2,x_2^2,x_3^2`$, for the bosonic case.

The eigenvalue of $`H_N^\pm `$ corresponding to the eigenstate labelled by $`x_1^{n_1}x_2^{n_2}\mathrm{}x_L^{n_L}`$ is given by $`_{\mathrm{}=1}^LE_{\mathrm{}}n_{\mathrm{}}`$, if $`E_{\mathrm{}}`$ denotes the $`\mathrm{}`$-th energy eigenvalue of the one-particle-Hamiltonian. Hence the corresponding eigenvalue of $`\mathrm{exp}(\beta H_N^\pm )`$, where, as usual, $`\beta =\frac{1}{k_BT}`$ denotes the inverse temperature, will be

$$\mathrm{exp}(\beta \underset{\mathrm{}=1}{\overset{L}{}}E_{\mathrm{}}n_{\mathrm{}})=(e^{\beta E_1})^{n_1}\mathrm{}(e^{\beta E_L})^{n_L}.$$
(1)
This eigenvalue is nothing else but the value of the monomial $`x_1^{n_1}x_2^{n_2}\mathrm{}x_L^{n_L}`$ evaluated at $`x_1=e^{\beta E_1},\mathrm{},x_L=e^{\beta E_L}`$. To obtain the trace $`\text{Tr}\mathrm{exp}(\beta H_N^\pm )`$ we have to sum over all eigenstates, or, equivalently, over all monomials of degree $`N`$ (subject to the constraint $`n_{\mathrm{}}=0,1`$ in the fermionic case). Interchanging summation and evaluation, we may first consider the bosonic polynomial $`b_N`$ (resp. the fermionic $`f_N`$) obtained by summing up all monomials of degree $`N`$ (satisfying the above constraint in the case of $`f_N`$) and then, in a second step, evaluate this polynomial at $`x_{\mathrm{}}=e^{\beta E_{\mathrm{}}},\mathrm{}=1,\mathrm{},L`$ in order to obtain $`\text{Tr}\mathrm{exp}(\beta H_N^\pm )`$. The latter is usually called the partition function of the system. In our example, $`b_2=x_1^2+x_2^2+x_3^2+x_1x_2+x_1x_3+x_2x_3`$ and $`f_2=x_1x_2+x_1x_3+x_2x_3`$. Both polynomials are symmetric w. r. t. any permutation of their arguments $`x_1,x_2,x_3`$. This also holds in the general case.

Thus we have established a connection between systems of $`N`$ non-interacting bosons (resp. fermions) and certain symmetric polynomials $`b_N`$ (resp. $`f_N`$). Specification of the one-particle Hamiltonian then corresponds to an evaluation of these polynomials at $`x_{\mathrm{}}=e^{\beta E_{\mathrm{}}},\mathrm{}=1,\mathrm{},L`$ and yields the particular partition function.

## 3 Symmetrical polynomials

We collect some well-known definitions and results on symmetric polynomials which are relevant for our purposes. Throughout we consider polynomials in a finite number of (symbolic) variables $`x_1,\mathrm{},x_n`$. Most results also hold for the case of infinitely many variables ($`n=\mathrm{}`$) which is of physical interest, where the polynomials become formal power series. We will only indicate those cases where $`n=\mathrm{}`$ becomes problematic.
A polynomial $`p`$ is called symmetric iff $`p(x_1,\mathrm{},x_n)=p(x_{\sigma (1)},\mathrm{},x_{\sigma (n)})`$ for all permutations $`\sigma 𝒮_n`$. The elementary symmetric polynomials $`f_m`$ can be defined through their generating function

$$\underset{\mathrm{}=1}{\overset{n}{}}(x+x_{\mathrm{}})=\underset{m=0}{\overset{n}{}}f_mx^{nm},m=0,\mathrm{},n.$$
(2)
For example,

$`f_0`$ $`=`$ $`1,`$ (3)
$`f_1`$ $`=`$ $`x_1+x_2+\mathrm{}+x_n,`$ (4)
$`f_2`$ $`=`$ $`{\displaystyle \underset{i<j}{}}x_ix_j,`$ (5)
$`\mathrm{}`$
$`f_n`$ $`=`$ $`x_1x_2\mathrm{}x_n.`$ (6)
The letter “f” for elementary symmetric polynomials is unusual, but chosen here to stress the association to “fermions”. One important property of the $`f`$’s is that $`(f_1,\mathrm{},f_n)`$ forms a basis in the sense that any symmetric polynomial can be uniquely written as a polynomial of the $`f_m`$. For example, if $`n=2`$,

$$x_1^2+x_2^2=(x_1+x_2)^22x_1x_2=f_1^22f_2.$$
(7)
Of course, there exist other bases of symmetric polynomials. For our purposes, the following ones are the most important:

Let $`b_{\mathrm{}}`$ denote the sum of all monomials of degree $`\mathrm{}`$, for example

$`b_0`$ $`=`$ $`1,`$ (8)
$`b_1`$ $`=`$ $`x_1+x_2+\mathrm{}+x_n,`$ (9)
$`b_2`$ $`=`$ $`{\displaystyle \underset{ij}{}}x_ix_j,`$ (10)
$`\mathrm{}`$
Obviously the $`b_{\mathrm{}}`$ are symmetric polynomials, sometimes called complete symmetric polynomials (our “b” refers to “bosons”). Also the sequence $`(b_0,\mathrm{},b_n)`$ forms a basis in the ring of all symmetric polynomials in $`n`$ variables, as we will see below. For example, if $`n=2`$,

$$x_1^2+x_2^2=2(x_1^2+x_2^2+x_2x_2)(x_1+x_2)^2=2b_2b_1^2.$$
(11)
Another basis is given by the power sums

$$s_{\mathrm{}}=\underset{i=1}{\overset{n}{}}x_i^{\mathrm{}},\mathrm{}=0,\mathrm{},n.$$
(12)
($`s_0=n`$ has to be redefined in the case $`n=\mathrm{}`$.) In order to prove that $`(s_0,\mathrm{},s_n)`$ forms a basis, it would suffice to show that every elementary symmetric polynomial $`f_m`$ could be expressed as a polynomial of the $`s_{\mathrm{}}`$. This, in turn, follows immediately from the Newton identities, as they are called in Ref. ,

$$mf_m=\underset{k=0}{\overset{m1}{}}(1)^{k+1}f_ks_{mk},1mn.$$
(13)
These identities could be viewed as recursion relations for the $`f_m`$. Iterative substitution then yields the $`f_m`$ solely in terms of the $`s_{\mathrm{}}`$, for example

$$f_3=\frac{1}{6}(s_1^33s_1s_2+2s_3).$$
(14)
Explicit formulae for these representations will be given below.

Now consider the case of the $`b_m`$. Here we have analogous identities which immediately imply that $`(b_0,\mathrm{},b_n)`$ will form a basis:

$$\underset{k=0}{\overset{m}{}}(1)^kf_kb_{mk}=0,1mn.$$
(15)
These identities can most compactly be written in terms of the generating functions

$`F(z)`$ $`={\displaystyle \underset{r=0}{\overset{\mathrm{}}{}}}f_rz^r`$ $`={\displaystyle \underset{\mathrm{}=1}{\overset{\mathrm{}}{}}}(1+x_{\mathrm{}}z),`$ (16)
$`B(z)`$ $`={\displaystyle \underset{r=0}{\overset{\mathrm{}}{}}}b_rz^r`$ $`={\displaystyle \underset{\mathrm{}=1}{\overset{\mathrm{}}{}}}(1x_{\mathrm{}}z)^1`$ (17)
as

$$B(z)F(z)=1.$$
(18)
Finally we give the explicit representations of the $`f_m`$ and $`b_m`$ in terms of the power sums $`s_{\mathrm{}}`$, as well as the representations of the $`f_m`$ in terms of the $`b_k`$ and vice versa. To write these representations in compact form, it is convenient to use partitions. A partition $`\lambda `$ of a positive integer $`N`$, written as $`\lambda N`$, is a way to write $`N`$ as a sum, irrespective of order, in other words, a non-increasing sequence of positive integers $`(\lambda _1,\lambda _2,\mathrm{},\lambda _p)`$ such that $`_{i=1}^p\lambda _i=N`$. $`\mathrm{}(\lambda )p`$ is called the length of a partition. Another notation for $`\lambda `$ is $`(1^{m_1}2^{m_2}\mathrm{})`$ where $`m_i`$ counts the occurence of the integer $`i`$ in the partition $`(\lambda _1,\lambda _2,\mathrm{},\lambda _p)`$. Further let $`\zeta (\lambda )(_{i=1}^pi^{m_i}m_i!)^1`$ and $`\mu (m)`$ denote the multinomial coefficient

$$\mu (m)\frac{(_im_i)!}{_im_i!}.$$
(19)
Products of special symmetric polynomials introduced above according to a partition $`\lambda `$ will be written with a subscript $`\lambda `$, for example,

$$f_\lambda \underset{\mathrm{}=1}{\overset{p}{}}f_\lambda _{\mathrm{}}.$$
(20)
Then

$$\begin{array}{c}b_N\hfill \\ f_N\hfill \end{array}\}=\underset{\lambda N}{}(\pm 1)^{N+\mathrm{}(\lambda )}\zeta (\lambda )s_\lambda ,$$
(21)
where the $`+`$sign refers to the $`b`$’s and the $``$sign to the $`f`$’s, and

$$\begin{array}{c}b_N\hfill \\ f_N\hfill \end{array}\}=\underset{\lambda N}{}(1)^{N+\mathrm{}(\lambda )}\mu (m)\{\begin{array}{c}f_\lambda \hfill \\ b_\lambda \hfill \end{array}.$$
(22)
Note the symmetry of the transformations $`fb`$ and $`bf`$. This is a consequence of the invariance of the identities (15) with respect to the interchange $`bf`$ and of $`b_0=f_0=1`$. Note that (22), according to (17), is essentially equivalent to a well-known explicit expansion formula for the reciprocal value of a power series. These and other explicit relations between special symmetric polynomials are often also written in terms of determinants, see .

## 4 Partition functions

The canonical partition function plays a fundamental role in statistical mechanics since most thermodynamic functions can be derived from it. It is defined by

$$Z(\beta )\mathrm{Tr}\mathrm{exp}(\beta H),$$
(23)
where $`H`$ denotes the Hamiltonian of the system. Sometimes one writes $`Z_N(\beta )`$ in order to stress the dependance on the number $`N`$ of particles in the system. The grand canonical partition function is defined by

$$𝒵(z,\beta )\underset{N=0}{\overset{\mathrm{}}{}}Z_N(\beta )z^N,$$
(24)
where the variable $`z`$ is physically interpreted as the fugacity of the system.

Here we will only consider ideal gases, i. e. the case where H is the sum of $`N`$ (identical) single-particle Hamiltonians

$$H=\underset{n=1}{\overset{N}{}}h_n,$$
(25)
for example, $`N`$ fermions in a common potential or mean field.

Let $`E_{\mathrm{}}`$ denote the energy eigenvalues of $`h_n`$, counted in such a way that several $`E_{\mathrm{}}`$ have the same value in case of degeneracy. Then the bosonic($`+`$) or fermionic($``$) partition functions depend only on the $`E_{\mathrm{}}`$ and can be written as

$$Z_N^{}(\beta )=\underset{i_1<i_2<\mathrm{}<i_N}{}\mathrm{exp}(\beta \underset{\mathrm{}=1}{\overset{N}{}}E_i_{\mathrm{}})$$
(26)
or

$$Z_N^+(\beta )=\underset{i_1i_2\mathrm{}i_N}{}\mathrm{exp}(\beta \underset{\mathrm{}=1}{\overset{N}{}}E_i_{\mathrm{}}).$$
(27)
Let us consider for the moment only systems with a finite number of energy eigenvalues $`E_1,\mathrm{},E_n`$. Expanding the exponentials in (26),(27) into products and introducing the abbreviations

$$x_{\mathrm{}}=\mathrm{exp}(\beta E_{\mathrm{}}),\mathrm{}=1,\mathrm{},n,$$
(28)
it is easy to see, c. f. section 2, that

$$Z_N^{}=f_N(x_1,\mathrm{},x_n),$$
(29)
and

$$Z_N^+=b_N(x_1,\mathrm{},x_n).$$
(30)
Hence the fermionic/bosonic partitions functions for particular systems are obtained if the corresponding symmetric polynomials $`f_N`$/$`b_N`$ are evaluated at the values (28), where only $`\beta `$ is left variable. The grand canonical partition functions obviously correspond to the generating functions of special symmetric polynomials introduced in (16). It is then obvious that suitable relations between symmetric polynomials can be translated into relations between partition functions which are independent of the particular physical system, e. g. of the common potential or the dimension of the physical space, as long as the systems are ideal gases.

For systems with infinite-dimensional Hilbert spaces, i. e. $`n=\mathrm{}`$, the polynomials degenerate into formal power series. Evaluation at the values (28) leads to partition functions only if these series converge. But then the translation of combinatorical results into physical ones is still possible.
Having identified the physical interpretation of the $`f`$’s and the $`b`$’s it remains to investigate the power sums $`s_j`$. Since $`x_{\mathrm{}}^j=\mathrm{exp}(j\beta E_{\mathrm{}})`$ we conclude

$$s_j(e^{\beta E_1},\mathrm{},e^{\beta E_{\mathrm{}}},\mathrm{})=Z_1^\pm (j\beta ).$$
(31)
Note that $`Z_1^+=Z_1^{}`$.

Now we can interprete all results mentioned in the last section as relations between the physical partition functions. We will not reproduce these relations anew but say a few words on each. The Newton identities (13) are viewed as recursion relations for partition functions which allow the explicit calculation of $`Z_N^\pm (\beta )`$ if $`Z_1(\beta )`$ is known for all $`\beta `$. In this context they appear for the first time in the textbook of P. Landsberg . Later they have been re-discovered and applied recently to systems of few quantum particles, see e.g. . An explicit representation equivalent to (21) appears within a physical context in  and . Equations (15) and (22) express relations between bosonic and fermionic partition functions which have, to our knowledge, not yet been considered in the physical literature. Note, however, that the identity (18) can be rewritten as

$$𝒵^+(z,\beta )𝒵^{}(z,\beta )=1,$$
(32)
which obviously follows from the product representations and is implicitely contained in the above-mentioned articles based on a “unified treatment” of Fermi and Bose statistical mechanics of ideal gases . We remark that (32) implies $`Z_1^+=Z_1^{}`$ which is closely related to the fact that in the classical limit (i. e. $`z0`$) the distinction between Fermi and Bose gases disappears. Further we note that from the product representation (16,17) and (18) one immediately derives the well-known fact that $`𝒵^{}`$ has zeros at $`z_{\mathrm{}}=\mathrm{exp}(\beta E_{\mathrm{}})`$ and no poles, and hence $`𝒵^+`$ has poles at $`z_{\mathrm{}}=\mathrm{exp}(\beta E_{\mathrm{}})`$ and no zeros. Poles and zeros lie outside the physical domain of $`z(0,\mathrm{})`$ for fermions and $`z(0,1)`$ for bosons.

## 5 Concluding remarks

In this article we have suggested a new way of looking at the partition functions of ideal quantum gases. The construction of these functions is split into two steps. In the first step we consider a finite or infinite set of abstract energy levels as symbolic variables and define certain symmetric polynomials (or formal power series) in these variables: the $`b_N`$ for bosons and the $`f_N`$ for fermions. The symmetry involved is a symmetry between energy levels, not between particles. It is due to the fact that for non-interacting particles all possible occupations of the energy levels are counted on an equal footing. This first step is the same for each physical system.

The second step consists in an evaluation of the symmetric polynomials $`b_N`$ and $`f_N`$ at the values $`e^{\beta E_{\mathrm{}}}`$ for the variable $`x_{\mathrm{}}`$. Only within this step the numerical energy values of the concrete physical systems, their degeneracies et cetera enter into the expression for the partition functions. Now the different possible occupations of the energy levels contribute to the partition function with different weights. The mentioned physically relevant combinatorical results are independent from the second step and hold for all considered systems.

Finally we would like to mention that the wording “partition function” is due to Darwin and Fowler  and is obviously connected to the “partition” of energy into the energy levels of a system. Thus the combinatorical element was present from the outset, although the connection to the combinatorical partitions occuring in the explicit formulae of section 3 seems to be novel.

## Acknowledgement

We thank Klaus Bärwinkel, Peter Landsberg, Howard Lee, Marshall Luban, Guy Melan on, and Fabrice Philippe for stimulating discussions and/or valuable hints.

## References


text:
# 1 (a) The electronic energy of CE phase per site via the on-site interaction; (b) and (c) the phase diagrams on a square lattice for 𝑈=0 and +∞, respectively .

Coulomb interaction and instability of CE-type structure in half-doped manganites

In their Letter, den Brink, Khaliullin, and Khomskii proposed theoretically that the one-dimensional ferromagnetic zigzag chains in CE phase in half-doped manganites play an essential role in forming the orbital ordering, and, more surprisingly, the on-site Coulomb interaction U between electrons with different orbitals leads to experimentally observed charge ordering. In this Comment, I point out that the strong U will destroy the stability of CE-type phase, which is stable in a very narrow regime in the parameter space for electronic model.

The same notations as in Ref.  are employed here. In Ref. , the case of $`U=0`$ was analyzed and CE phase was found to be stable when the superexchange coupling $`J>0.1524t`$ (t is the hopping integral). In the CE phase the one-dimensional zigzag chain consists of two types of lattice sites, the bridge and corner sites. The bridge site is occupied singly by electrons with certain orbitals while the corner sites can be occupied doubly. Without U, the charge distribution along the zigzag chain is uniform, i.e., 1/2. Finite U will push the charge away from the corner sites to the bridge sites to form charge ordering. The theory explains the patterns of three orderings almost perfectly. We observe that the U will also increase the energy of the CE phase. The rod-type (i.e., C-type) phase consists of one-dimensional ferromagnetic straight chains. The chains are occupied at most singly on each site. Thus the U does not change the energy of the C-type phase. This fact leads to the instability of CE phase with respect to C-type phase for finite U. We evaluate the electronic energy for CE phase by using exact diagonalization method. The energies from the magnetic coupling are the same for both C-type and CE phase. At $`U=0`$, $`E_{kin}^{CE}=0.6953t`$ for CE-type phase and $`E_{kin}^C=0.6366t`$ for C-type phase. However, at $`U=+\mathrm{}`$, $`E_{kin}^{CE}=0.61t`$ and the energy of C-type phase keeps unchanged. In other words, the CE phase is unstable with respect to C-type phase when electron correlation becomes stronger. Numerical results for energies of CE phase via the U is shown in Fig. 1(a). The calculation is performed on 8-, 12- and 16-site chains, respectively. The size-effect is very small. The main reason is that the half-doped zigzag chain is a band insulator. This is also seen from the calculation of $`E_{kin}^{CE}`$ for a finite chain when $`U=0`$. Its value for 16 sites is -0.695328t, which is equal to the value of an infinite chain up to the order of 10-6. At about $`U5t`$, the CE-type phase has a higher energy than C-type phase. To establish a comprehensive phase diagram, we have to consider other possible phases. Except for conventional anti- and ferromagnetic phases, a novel type of phase is taken into account. The phase consists of two-site ferromagnetic valence bonds (VB), and the bonds couple antiferromagnetically. Electrons are localized within the bonds. The electronic part of the state in a valence bond is $`\frac{1}{\sqrt{2}}(c_{i,\alpha ,\sigma }^{}+c_{j,\alpha ,\sigma }^{})|0`$, and the local spins are parallel to spin of electron. The energy per site is $`E_{kin}^{VB}+E_{mag}^{VB}=0.5tJ`$, which is independent of U (we take the magnetic energy as zero for CE phase). The ferromagnetic phase has energy $`t+2J`$ for three dimension and $`0.919t+2J`$. Thus when $`U=0`$ and $`0.152tJ0.195t`$ for three dimension and $`0.117tJ0.195t`$ for two dimension, CE phase has a lower energy. The phase diagrams for $`U=0`$ and $`U=+\mathrm{}`$ as shown in Fig.1(b) and (c) are evaluated on a 4$`\times `$4 lattice with a periodic boundary condition by means of combination of mean field theory and exact diagonalization. We assume the magnetic structure and claculate the energy by exact diagonalization. FM and C-AF are assumed to contain two sublattices and evolve into G-AF when spins on two sublattices are not parallel for large J. Thus, the CE phase does not appear in the ground state for the model in Ref.  in the case of strong correlation.

In doped manganites, U is usually estimated to be much larger than t. In Ref. , $`U10t`$. The on-site U alone can produce the experimentally observed pattern of charge ordering, but cannot stabilize the CE phase. To solve this issue finally, we have to take into account other interactions, such as the long-range Coulomb interaction, Jahn-Teller distortion, and physics of topological berry phase. For example, the effect of finite large JH leads to an attractive particle-hole interaction, which favors to stabilize the charge ordering.

This work was supported by RGC grant of Hong Kong.

Shun-Qing Shen

Department of Physics, The University of Hong Kong, Hong Kong and Institute of Physics, Chinese Academy of Science, P. O. Box 603, Beijing 100080, China


text:
# Dependence of the flux creep activation energy on current density and magnetic field for MgB2 superconductor

## Abstract

Systematic ac susceptibility measurements have been performed on a MgB2 bulk sample. We demonstrate that the flux creep activation energy is a nonlinear function of the current density $`U(j)j^{0.2}`$, indicating a nonlogarithmic relaxation of the current density in this material. The dependence of the activation energy on the magnetic field is determined to be a power law $`U(B)B^{1.33}`$, showing a steep decline in the activation energy with the magnetic field, which accounts for the steep drop in the critical current density with magnetic field that is observed in MgB2. The irreversibility field is also found to be rather low, therefore, the pinning properties of this new material will need to be enhanced for practical applications.

The recent discovery of the new superconductor MgB2  with its transition temperature at 39K has aroused considerable interest in the field of condensed matter physics, especially in the area of superconductivity. Intensive studies have been carried out on this new material by means of magnetic  and transport  measurements, microstructure studies , and other experimental techniques , as well as theoretical calculations . The fundamental superconducting parameters of MgB2 such as the upper critical field $`B_{c2}(0)=12.518`$ T , the lower critical field $`B_{c1}(0)300`$ Gs , the Ginzburg-Landau parameter $`\kappa 26`$ , the coherence length $`\xi (0)=45.2`$ nm , the penetration length $`\lambda (0)=140180`$ nm , and the energy gap $`\mathrm{\Delta }(4.2\mathrm{K})=4.35.2`$ meV  have been obtained. The critical current density, one of the most important parameters in considering superconductors for practical applications, has been determined to be about $`10^6`$ A/cm2 at 0 T and 4.2 K in bulk samples  and $`8\times 10^6`$ A/cm2 at 0 T and 5 K in thin films . The critical current density is determined by the pinning properties of the sample as well as by the flux motion, because the motion of the vortices over pinning centers (flux creep) in the superconductor induces dissipation and reduces the critical current density $`j_c`$. It is the flux creep that sets the limiting critical current density in superconductors. It is thus essential to study the activation energy against flux motion, in order to understand the underlying mechanism and therefore to enhance the current carrying capacity of this new material. In this paper, we investigate the flux creep activation energy in MgB2, and determine its dependence on the current density, the magnetic field, and the temperature by measuring the real $`\chi ^{}(T)`$ and imaginary $`\chi ^{\prime \prime }(T)`$ parts of the ac susceptibility at different ac field amplitudes, frequencies and dc magnetic fields.

All measurements have been performed on a MgB2 bulk sample, which was prepared by conventional solid state reaction . High purity Mg and B (amorphous) were mixed and finely ground, then pressed into pellets 10 mm in diameter with 1-2 mm thickness. Extra Mg was added in order to avoid Mg loss at high temperatures. These pellets were placed on an iron plate and covered with iron foil, then put into a tube furnace. The samples were sintered at temperatures between 700 and 1000oC for 1-14h. A high purity Ar gas flow was maintained throughout the sintering process. A sample with dimension of $`2.18\times 2.76\times 1.88`$ mm3 was cut from the pellet. Phase purity was determined by XRD and grain size by SEM. Only a small level of MgO was found and the grain size was determined to be about 200 $`\mu `$m.

The ac susceptibility measurements were carried out using a superconducting quantum interference device (SQUID, Quantum Design PPMS 8 T). The superconducting transition temperature $`T_c=38.6`$ K, $`\mathrm{\Delta }T_c<1`$ K was determined by ac susceptibility in an ac field of 0.1 Gs and frequency 117 Hz.

Fig. 1 shows the effects of the dc magnetic field $`B_{dc}`$ on the ac susceptibility of the MgB2 bulk sample. As $`B_{dc}`$ is increased from 0.5 T to 3 T, the transition temperature shifts to lower temperatures and the transition width broadens. Although the transition width is slightly changed from about 3 K at 0.5 T to 6 K at 3 T, the transition temperature is greatly depressed by the dc field from about 35 K at 0.5 T to 27 K at 3 T, while in YBCO, the depression in $`T_c`$ is quite small . As the transition temperature under a dc magnetic field is an indication of the irreversibility line, this result indicates that the irreversibility line in the MgB2 bulk sample is rather low in the H-T plane, similar to the results obtained by dc magnetization measurements .

Shown in Fig. 2 are typical $`\chi ^{}(T)`$ and $`\chi ^{\prime \prime }(T)`$ curves for the MgB2 bulk sample at $`B_{dc}`$=1 T, $`f=1117`$ Hz and different ac field amplitudes $`B_{ac}`$ indicated. As $`B_{ac}`$ is increased, the transition shifts to lower temperatures with increased width. In Fig. 3, we show the effects of the frequency on the ac susceptibility of this MgB2 bulk sample. Contrary to the effects of $`B_{ac}`$ and $`B_{dc}`$, as $`f`$ is increased, the transition shifts to higher temperatures and the transition width broadens. All the characteristics shown in Figs. 1,2,3 for the MgB2 bulk sample are similar to what have been observed in high temperature superconductors  and predicted from theoretical calculations . This is understandable, because ac susceptibility at different dc magnetic fields, ac field amplitudes and frequencies reflects a common phenomenon, i.e., flux dynamics in type-II superconductors.

A measurement of the superconducting transition by means of the ac susceptibility $`\chi =\chi ^{}+i\chi ^{\prime \prime }`$ typically shows, just below the critical temperature $`T_c`$, a sharp decrease in the real part of the susceptibility $`\chi ^{}`$, a consequence of diamagnetic shielding, and a peak in the imaginary part of the susceptibility $`\chi ^{\prime \prime }`$, representing losses. The peak in $`\chi ^{\prime \prime }`$ will occur when the flux front reaches the center of the sample. It follows that the position of the peak in $`\chi ^{\prime \prime }`$ will also strongly depend on temperature, dc field, ac field amplitude and frequency. The criterion for the peak in $`\chi ^{\prime \prime }`$ is

$$U(T_p,B_{dc},j)=k_\mathrm{B}T_p\mathrm{ln}\frac{1}{f_{\mathrm{peak}}t_0}$$
(1)
where the time scale $`t_0=4\pi \mu _0H_{ac}^2/\rho _0j^2(\omega )`$ , $`\rho _0`$ is the prefactor in the Arrhenius law $`\rho =\rho _0\mathrm{exp}[U(j)/k_\mathrm{B}T]`$, $`T_p`$ is the peak temperature in the $`\chi ^{\prime \prime }(T)`$ curve and $`k_\mathrm{B}`$ the Boltzmann constant.

It has been shown  by numerical calculation that during the penetration by the ac magnetic field into a superconductor, the magnetic field profile can be regarded as a straight line, so at the peak temperature the current density can be approximated as

$$j=\frac{H_{ac}}{d}$$
(2)
where $`d`$ is the sample size.

A plot of $`\mathrm{ln}f_{\mathrm{peak}}`$ versus $`U(T_p)/k_\mathrm{B}T_p`$ should thus be a straight line with the slope of $`U(j,B_{dc})`$,

$$\frac{U(T)}{k_\mathrm{B}T}U(j,B_{dc})=\mathrm{ln}(f)\mathrm{ln}(t_0)$$
(3)
By varying the ac amplitude and then using Eq.(2) to determine the current density, one can then reconstruct the current density dependence of the activation energy $`U(j)`$. Using the ac method the usual difficulty in conventional relaxation measurements of having only a very limited time window ($`110^4`$ s) can be overcome by extending the latter to smaller values of $`10^510^3`$ s ($`f=100`$ kHz $``$ 1 kHz) .

In order to account for the explicit temperature dependence of the activation energy, we choose a form of temperature scaling function

$$U(T)=[1(T/T_x)^2]^2$$
(4)
where $`T_x=36.3,34.3,31.5,29.1`$ K for $`B_{dc}=0.5,1,2,3`$ T respectively is a characteristic temperature, which is taken from the magnetic irreversibility line. $`U(T)`$ changes slightly with temperature for $`TT_x`$ and drops rapidly as T approaches $`T_x`$. A detailed discussion on choosing the function $`U(T)`$ has been given by McHenry et al .

Fig. 4 shows $`\mathrm{ln}f_{\mathrm{peak}}`$ versus $`U(T_p)/k_\mathrm{B}T_p`$ curves at $`B_{dc}=0.5`$ T and various current densities. The experimental data can be fitted very well by straight lines (Eq.(3), solid lines in Fig.4). We can then derive the activation energy $`U(j,B_{dc}=0.5\mathrm{T})`$ from the slopes of the straight lines. $`U(j,B_{dc})`$ at other dc magnetic fields have also been derived, and the results are summarized in Fig. 5, where the activation energy $`U(j)U(j,B_{dc})\times B^{1.3}`$ is plotted as a function of the current density for the MgB2 bulk sample at various dc magnetic fields. As can be seen from Fig. 5, we have obtained a universal curve $`U(j)`$ by scaling the data by $`B^{1.3}`$. The slight scattering at low current density may result from the field dependent critical current density $`j_c(B)`$. Note that $`B_{ac}`$ has been changed to $`j`$ by using Eq.(2), where $`d`$ is the sample size rather than the grain size, because it has been reported  that current flow in MgB2 is strongly linked. The current density $`j`$ obtained here is also very closed to what has been derived using magnetization measurements .

From the best fit of the data in Fig. 5, we derived the current density dependent activation energy $`U(j)j^{0.2}`$, which is highly nonlinear. This result suggests that the I-V curve of MgB2 should also be highly nonlinear, because using the Arrhenius rate equation, we have $`E=Bv_0=Bv_0\mathrm{exp}(U(j)/k_\mathrm{B}T)\mathrm{exp}(j^\mu )`$. Nonlinear $`IV`$ characteristics have been experimentally observed in MgB2 . On the other hand, the relaxation of the current density or the magnetization can be derived from Eq.(1) as $`j(t)[\mathrm{ln}(t/t_0)]^{1/\mu }`$, which is also a nonlinear function of $`\mathrm{ln}(t/t_0)`$. This nonlogarithmic relaxation can be detected by means of dc magnetization relaxation measurements, which will be discussed in one of our forthcoming works.

As can be seen from Eq.(3), with the current density $`j`$ fixed, we can also derive the activation energy as a function of the dc magnetic field $`U(B)`$. The results are summarized in Fig. 6, where the activation energy $`U(B)U(j,B_{dc})\times j^{0.21}`$ is plotted as a function of the magnetic field for the MgB2 bulk sample at various current densities. As can be seen from Fig. 6, we have also obtained a universal curve by scaling the data by $`j^{0.21}`$. This current density dependence is consistent with the one derived in Fig. 5. As the scaling factor $`B_0`$ (see Eq.(5) below) for $`B`$ is current density independent, we can see that the scaling of $`U(B)`$ is much better than that of $`U(j)`$ shown in Fig. 5. The solid line in Fig. 6 is a fit to the power law $`U(B)B^{1.33}`$. The obtained $`U(B)`$ is also consistent with the one derived from scaling in Fig. 5. The self-consistent scalings of $`U(j,B)`$ shown in Fig. 5 and Fig. 6 suggest that the separation of the activation energy $`U(j,B,T)`$ to $`U(j)U(T)U(B)`$ is quite reasonable. The final expression for the temperature, field and current density dependent activation energy is given by

$$U(T,B,j)=U_0\left[1\left(\frac{T}{T_x}\right)^2\right]^2\left(\frac{B}{B_0}\right)^n\left(\frac{j_0}{j}\right)^\mu $$
(5)
where $`U_0`$, $`B_0`$ and $`j_0`$ are scaling values, and the exponents $`n`$ and $`\mu `$ are determined to be 1.33 and 0.2 respectively.

As for the magnetic field dependence of the activation energy, a $`B^1`$ dependence has been previously derived using the Anderson-Kim model of the activation energy combined with the Ginzburg-Landau expressions for the coherence length, thermodynamic critical field and depairing critical current density, etc. . Such a $`B^1`$ dependence has been observed in a La1.86Sr0.14CuO4 single crystal with weak pinning centers by McHenry et al. . And for YBa2Cu3Ox samples with strong pinning centers, such as twin planes, stacking faults or Y2BaCu$`O_5`$ inclusions, a $`U(B)B^{0.5}`$ has been derived by both ac susceptibility  and dc magnetization measurements .

For the new superconductor MgB2 on the other hand, we find a $`U(B)B^{1.33}`$ dependence, showing that the activation energy decreases even faster with increasing magnetic field, compared to weakly pinned high temperature superconducting La1.86Sr0.14CuO4 single crystal. The weakening of the activation energy with increasing magnetic field may be the reason why the critical current density drops steeply as the magnetic field increases, as has been observed by dc magnetization measurements . Taking into account the relatively low irreversibility line (Fig. 1) and the weakening of the activation energy with increasing magnetic field, the pinning properties of MgB2 need to be enhanced for practical applications.

In summary, we have performed systematically ac susceptibility measurements on a MgB2 bulk sample. The magnetic field and current density dependent flux creep activation energy has been determined to be $`U(j,B)j^{0.2}B^{1.33}`$. Compared to high temperature superconductors $`U(B)B^1`$ for weakly pinned La1.86Sr0.14CuO4 single crystal and $`U(B)B^{0.5}`$ for strongly pinned YBa2Cu3Ox, the steeply declining dependence $`U(B)B^{1.33}`$ results in a steep drop in $`j_c`$ with magnetic field and suggests that pinning in MgB2 is quite weak, as can also be seen from the low irreversibility field.

The authors would like to thank Australian Research Council for financial support.


text: # Diffeomorphisms, Isotopies and Braid Monodromy Factorizations of Plane Cuspidal Curves