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# Band structure calculations for Ba6Ge25 and Ba4Na2Ge25 clathrates

## I Introduction

Ba6Ge25 clathrateBa6Ge25 ; Kim ; Fukuoka  attracted considerable scientific interest and initiated an intense experimental activity because of its rich physical properties. This class of compounds is investigated primarily because of their thermoelectric properties.Nolas  The concept of PGEC, phonon-glass electron-crystal, was introduced. Massive alkali and alkali-earth metal atoms are expected to rattle in oversized cages usually formed by Si, Ge or Sn atoms. Thus, they scatter the lattice phonons and reduce the thermal conductivity. On the other hand, electrical conductivity is believed to be more constrained to the cage and not much affected by rattling.

Ba6Ge25 undergoes a two-step first order structural phase transition at temperatures 215 and 180 K. Paschen ; Silke  The structural phase transition is accompanied by dramatic change of transport properties. Above the transition it shows a metal-like conductivity with fairly large value for this class of compounds. At the phase transition this behaviour is profoundly changed; resistivity abruptly increases, then slowly rises with lowering the temperature and saturates at low temperatures. The Hall coefficient smoothly decreases with decreasing the temperature and is not remarkably affected by the phase transition. Magnetic susceptibility is negative and temperature independent above and abruptly decreases at the phase transition similarly to the thermopower. Paschen ; Silke  It has been observed that hydrostatic pressure suppresses the phase transition.Malte  The homologue clathrate Ba4Na2Ge25,Na2Ba4Ge25  with smaller lattice parameter, does not undergo a phase transition and shows typical metal-like behaviour.Silke  At low temperatures both clathrates experience superconducting transitions. Malte

In this article we consider the electronic band structure of the compounds and the influence of the structural phase transition on the electronic band structure as well as the possible consequences on the transport properties. In Section II some structural details are considered. Details of the calculations are described in Section III. The results and the discussion are presented in Section IV. Finally, the summary and the conclusions are given in Section V.

## II Structure

The structure of Ba6Ge25 belongs to the space group $`P4_132`$ (No. 213). There are 124 atoms in the unit cell. All the structural details can be found in Ref. Ba6Ge25, ; Na2Ba4Ge25, ; Grin, ; Grin2, . Thorough description of the structure can also be found in Ref. Fassler2, ; Fassler,  on structurally similar Sn clathrates. Germanium atoms form the framework which defines three different types of cages filled with barium atoms. The main building blocks are distorted germanium pentagon-dodecahedra with Ba1 atoms inside. They form a chiral network with large cavities, where Ba2 and Ba3 atoms are placed. In the Ba4Na2Ge25, two sodium atoms are randomly distributed in three Ba2 sites per formula unit. In total, 17 of 25 germanium atoms per formula unit are four-fold coordinated by other germanium atoms. The remaining 8, usually denoted as Ge3 and Ge5, are three-fold coordinated. The average distance between germanium atoms ($``$2.54 Å) is somewhat larger than for Ge in diamond type structure ($``$2.45 Å) and the angles are distorted. Typical nearest distance between barium and germanium atoms is around 3.5 Å. The nearest distance between barium atoms is around 4.70 Å for Ba2-Ba3 in undistorted structure (see also Ref. Grin2, ).

Due to highly aspherical electron density deduced from X-ray diffraction data, split positions for Ba2 and Ba3 atoms are assumed. The most pronounced effect at the structural phase transition is the increase of the atomic displacement parameter for Ba2, and somewhat less for Ba3 atom. Grin ; Grin2  It is believed that below the phase transition Ba2 and Ba3 atoms are actually locked in the split sites. However, since no superstructure is observed, they should be randomly distributed among split sites. The germanium cage also undergoes modifications at the phase transition and there is not only a difference between the room temperature and the low temperature structure, but also the variation with temperature through the whole temperature range.Grin2

## III Computational details

Band structure calculations were performed within Local Density Approximation (LDA) using Linear Muffin Tin Orbital (LMTO) method in Atomic Sphere Approximation (ASA) with combined correction terms taken into account.Andersen ; Skriver  Scalar relativistic version was used with von Barth-Hedin exchange-correlation potential.Barth

The calculations for the room- and the low-temperature structural data for Ba6Ge25 were performed. The atomic parameters for different models used in calculations are given in Table 1. The barium atoms were placed in their average positions within higher symmetry model, i.e., space group $`P4_132`$. In Ba4Na2Ge25, the random distribution of the Na and Ba atoms at Ba2 site was neglected and the calculations were performed for lower symmetry model, namely, group $`P4_12_12`$ (No. 92), with sodium atoms at one of the 8$`b`$ symmetry sites.

The calculations with Ba2 and Na atoms shifted from their average positions in the original space groups (No. 213 and No. 92, respectively) were performed using lower symmetry models in space groups $`P2_13`$ (No. 198) and $`P4_1`$ (No. 76), respectively. In this way the assumed randomness of the locking was not considered.

Most of the results presented in this work were obtained from self-consistent calculations on $`12\times 12\times 12`$ k-space mesh. For the detailed band structure around Fermi level the calculations were performed for the $`16\times 16\times 16`$ mesh. The values of the DOS at the Fermi level for these cases showed corresponding variations of about 1 $`eV^1`$ per unit cell. The total energy was negligibly affected by this change of the mesh size.

The atomic sphere radii were determined so that their overlap was minimised. This resulted in the radii of about 1.5 Å (2.9 a.u.) for germanium and 2.5 Å (4.8 a.u.) for barium atoms. It is worth to note that, as the radii of germanium spheres are rather small, germanium $`p`$-states extend far beyond the sphere boundaries. The large part of these states, so called ”tails,” reside in the neighbouring barium spheres. This should be taken into account when considering barium and germanium charges which are defined as the integrals of the electron density over the corresponding sphere. They are clearly identified in the empty spheres of hypothetical $`\mathrm{}_6`$Ge25, where the barium atoms are replaced by the empty spheres of the same radii. In this case a high electron density near the boundary can be observed which diminishes toward the center of the empty sphere. Because of the large barium spheres, also the states of $`f`$-symmetry were used in the expansion of the wave function. In the germanium spheres the wave function was expanded up to the states of $`d`$-symmetry.

## IV Results and discussion

Here we present and discuss the results for the low temperature structure of Ba6Ge25 at 10 K, first with Ba atoms in the average sites. We focused the analysis on the density of states and the bonding properties between the barium atoms and the germanium cage. No distinctive qualitative difference in the DOS between the room and the low temperature structures within higher symmetry model was found. Further, we investigated the effects of shifting the barium atoms toward split positions on the band structure. This was done within the low temperature structure, because there the split positions are the most distant and the locking of the barium atoms is assumed. Finally, the results for the Ba4Na2Ge25, which does not undergo phase transition, are discussed. In particular, the influence of the sodium on the band structure is examined in comparison with barium.

### IV.1 Electronic band structure and density of states

The electronic band structure with its density of states calculated for Ba6Ge25 in the low temperature undistorted structure are shown in Fig. 1.

The overall picture is similar for the room temperature structure. Due to the large number of atoms in the unit cell there is a large number of bands and a complex electronic band structure.

In Fig. 2 the $`l`$-projections of DOS in germanium atomic spheres are shown: Ge in diamond structure, hypothetical Ge-graphite, $`\mathrm{}_6`$Ge25, and Ba6Ge25 compounds are compared. In the DOS, $`s`$-, $`sp`$-, and $`p`$-bonding regions can be recognised in filled and empty clathrate similar to those in Ge-diamond or graphite. This similarity is to be expected since locally 17 of 25 germanium atoms per formula unit are four-fold coordinated (4b) and form covalent $`sp^3`$-like bonds, like in the diamond structure. The other 8 germanium atoms are three-fold bonded (3b) more like in graphite structure.

The total width of the bonding region is about 0.9 eV narrower in the empty and filled clathrates. The fundamental gap between bonding and anti-bonding region is larger in $`\mathrm{}_6`$Ge25 than in the diamond structure by the same amount of 0.9 eV and there appears a gap between $`sp`$\- and $`p`$-like bands in the valence region. These features are common for the other Ge and Si clathrates (e.g., Ref. Dong, ). The appearance of the gap in the valence region by its contraction was associated with the 5-ring patterns (pentagons) of germanium or silicon atoms,Saito ; Moriguchi  but there was also some criticism of the idea.Moriguchi2  According to the latter, the small angular distortion of the tetrahedrally bonded framework may also play an important role. While for Ge clathrates of type I and II an overlap of the $`s`$\- and $`sp`$-region is observed,Dong  here one can see a clear separation. One should keep in mind that in Ba6Ge25 structure, in contrast to the clathrates I and II, there are three bonded germanium atoms. However, the band structure calculation on hypothetical Ge-graphite, where all germanium atoms are three-fold coordinated, did not reveal pronounced tendency toward such a separating of the $`s`$\- and $`sp`$-regions, as seen in Fig. 2.

The main difference in the site projected DOS for germanium atomic spheres between the empty and the filled clathrate is the reduction of the gap between bonding and anti-bonding region in the filled clathrate. This immediately shows the importance of barium atoms not only as the pure electron donors to the conduction band formed of germanium anti-bonding states.

The three-bonded germanium atoms, six Ge5 and two Ge3, form a distorted cube around Ba3. Ba2 atoms lie on the lines passing from the central Ba3 through the cube faces formed by three Ge5 and one Ge3 atom. In this way they form a large octahedron around Ba3. The closest distances are between Ba2 and Ge3, 3.35 Å, and Ba3 and Ge5 3.38 Å. Ge3 atoms are somewhat more distant from Ba3, at 3.89 Å. This environment and the nature of the bonds between Ba3, Ge3, Ge5, and Ba2 should be the key to understand the physical properties of the compound and its phase transition.Grin2

Let us consider the charges in the atomic spheres. As mentioned in Section III, there is a large contribution of germanium states in the oversized barium spheres. This can be seen in Table 2 in the column for the charges of empty clathrate, $`\mathrm{}_6`$Ge25.

The large charges in the empty spheres are coming from the tails of germanium states. The highest value is in $`\mathrm{}`$1. This is expected because $`\mathrm{}`$1 has the closest Ge neighbours forming distorted pentagon-dodecahedron. Despite of the fact that $`\mathrm{}`$3 has the largest sphere, relatively smaller charge is found inside due to the fewer Ge neighbours. For three-bonded germanium atoms it can also be noted that they have somewhat smaller charges inside their spheres in comparison to the four-bonded germanium, although e.g., Ge3 has the largest atomic sphere from all germanium atoms. Among germanium atoms, three-bonded Ge3 and Ge5 have the largest increase of the charge upon inclusion of barium atoms. This is in accord with the expectation of Zintl concept, namely, that three-bonded germanium atoms accept an electron from barium atoms to form the lone electron pairs. However, because of the small germanium spheres the absolute value of the difference is not so pronounced. Among barium spheres, the largest increase of the charge, in comparison to the corresponding empty spheres, undergoes the Ba3 sphere. We interpret this as the influence of the lone pairs, reflected in the Ba3 sphere as the tails from neighbouring three-bonded germanium atoms. This is illustrated in Fig. 3 where the differences of the $`l`$-projected radial charge densities in the several atomic spheres are shown. The large electron density near the boundary of Ba3 atomic sphere may be associated with the lone electron pairs of the neighbouring three-bonded germanium atoms. It was also shown by electron localisation function (ELF) analysis that these lone pairs are situated around Ba3 site.Grin2  The oscillating part of the density, i.e., its difference shown in Fig. 3, may be interpreted as more atomic-like barium states. The biggest contribution comes from the states of $`d`$-symmetry.

We conclude that there is only a small charge transfer from barium to the cage, just in agreement with conclusion made for Ba8Ga16Ge30 in Ref. Blake2, , with difference, that here all the arguments point out that a considerable amount of the electron charge remains in the states with significant barium character. This is in contrast to the situation reported for K8Ge46 in Ref. Zhao,  where the authors conclude complete charge transfer from potassium atom to the frame. Both of these cited results were critically re-considered and charge transfer redefined in the recent paper. Nagano  However, as may be seen in Fig. 3, the large amount of the charge in the barium spheres resides near the boundaries, so that it may be said that the conduction electrons are more constrained to the cage.

In the band structure calculations for the similar K6Sn25 and K6Sn23Bi2 compounds, a lifting of the three bands, originated only from three-bonded tin atoms, from the top of the valence region was found and ascribed to the interaction of the lone pairs formed by three-bonded tin atoms. Fassler . But, as was pointed out there, in Ba6Ge21In4 this characteristic is absent due to a smaller spatial extension of germanium orbitals. We did not notice significant difference of DOS between three-bonded (Ge3, Ge5) and four-bonded germanium atomic spheres. However, as discussed above, we expect that the lone electron pair states mostly reside as tails in $`\mathrm{}`$3 atomic sphere. Therefore one might expect their contribution to the DOS in $`\mathrm{}`$3 sphere in $`\mathrm{}_6`$Ge25. Indeed, we find a peak in DOS on the top of the unoccupied valence region (Fig. 4) appearing only in $`\mathrm{}`$3 sphere. This peak remains in the filled clathrate, i.e., in Ba3 sphere, what can also be seen in Fig. 4. For Ba2 and Ba3 spheres a large increase of DOS, compared to the empty $`\mathrm{}`$2 and $`\mathrm{}`$3 spheres, in the region around the Fermi energy is found. The number of states is increased and this suggests that the barium states participate in the conduction band formation.

This is in contrast to the results for the Ba8Ga16Ge30 clathrate Blake2  where the inclusion of barium atoms inside the Ga-Ge cage left the band structure almost intact. This is also different to the cases of some Si clathrates Demkov  where the main effect of the inclusion of alkali metal was shifting of the particular state at the bottom of the conduction band, but still predominantly of the cage-like character so that it was possible to neglect the overlap of the orbitals of guest atoms with host-cage. Here, however, the distances between the barium and germanium atoms are shorter and stronger hybridisation may be expected.

Another important feature of DOS is that it shows a peak just at the Fermi level (Fig. 5). Its value is around 50 states/eV per unit cell in the low temperature structure. The largest contributions come from barium atomic spheres mainly with $`d`$-symmetry and from $`p`$-states in germanium atomic spheres. The shape of the DOS coming from barium and germanium spheres follows closely each other. This indicates a strong hybridisation of barium and germanium states. The contribution from Ba1 spheres is significantly lower than that from Ba2 and Ba3 spheres, although Ba1 has the nearest Ge neighbours. This complies with the assumption that the Ba2 and Ba3 atoms with the surrounding three-bonded germanium atoms determine the most unusual properties of the system. It is quite interesting that the similar peak of the DOS at the Fermi energy was found for Ba8Si46 clathrate Moriguchi ; Saito  as well. In that case also the relatively shorter distances between the barium and silicon atoms were found ($``$3.3-3.5 Å). We have also performed calculation for Ba6Si25.Fukuoka2  The lattice parameter is smaller compared to the Ge clathrate and the fundamental gap disappears completely but the peak in the DOS at the Fermi level with strong contribution of the states with $`d`$-symmetry coming from the barium atomic spheres remains (Fig. 5). It is also interesting that the subband-gap between $`s`$\- and $`sp`$\- regions (not shown in the Fig. 5) appears in the Ba6Si25 as well.

For a better understanding of the above results, i.e., the role that is played by barium states, we have performed the calculation with barium atoms only, Ba$`{}_{6}{}^{}\mathrm{}_{25}^{}`$, without the Ge framework. The distances between Ba2 and Ba3 atoms of about 4.70 Å are comparable to the distances between atoms in Ba bcc structure with 4.34 Å. The calculation showed the dominant contribution of $`d`$-symmetry states at the Fermi level. The $`s`$-states are split into bonding and the anti-bonding regions. The bonding states lie below Fermi level and anti-bonding above, so that they do not give significant contribution to the DOS at the Fermi level. The tails of the barium $`d`$-states in the empty germanium spheres are of $`s`$\- and $`p`$-symmetry, so that the appreciable overlap of these states with germanium $`s`$\- and $`p`$-states in the filled clathrate might be expected. Concerning the relative energy parameters of the barium and germanium muffin-tin orbitals, they showed qualitative agreement with the values used for the atomic orbitals in LCAO calculations. Harrison  All these facts suggest that the appearance of the barium $`d`$-states and their hybridisation with germanium $`p`$-states at the Fermi level is quite plausible.

The possible importance of the hybridisation of the Ba 5$`d`$ states with Si cage was also pointed out for Ba8Si46.Saito  The results of the experiment with ultrahigh-resolution photoemission spectroscopy for Ba8Si46 suggest even stronger hybridisation of Ba and Si states than obtained in LDA calculation. Yokoya  NMR experiments on this compound could be interpreted if strong contribution of Ba $`d`$-states to the DOS at the Fermi energy is assumed. Shimizu

### IV.2 Band structure near the Fermi level versus Ba2 shift

The presence of the peak in the DOS at the Fermi level suggests a possible instability of the system. Since there are strong indications of locking of Ba2 atoms at the phase transition, as mentioned in Section II, we investigated the modifications of the band structure due to the shifting of Ba2 atoms within the low temperature structure.

The most interesting effect of this shifting of Ba2 atoms, performed as explained in Section III, is the splitting of the peak at the Fermi level and, consequently, the reduction of DOS. The effect was found to be the most pronounced with Ba2 at 80% distance from the higher symmetry position toward the experimental split position. In Fig. 6, the band structure together with the DOS in the close vicinity of the Fermi level for this structure is compared with the higher-symmetry (average) structure. The effect may be considered as a band Jahn-Teller effect, though in the band structure along the symmetry directions no obvious removing of the degeneracy is observed. The equivalent scenario was proposed for some other compounds with somewhat similar metal-insulator transition. Hagino  The conventional Jahn-Teller effect was considered also for some other clathrates. Demkov ; Tse ; Brunet

The total energy was also compared for shifted positions. The minimum was found to be at the off average position. The potential energy surface for Ba atoms showed binding stronger than expected, but the variation of the total energy with respect to the shifting of atoms is known not to be highly accurate within the atomic sphere approximation. That is also the reason why the structure optimization was not performed.

One has to be careful with the interpretations, especially because the whole framework is slightly changing with the temperature and is strongly disturbed during the phase transition. Grin2  As mentioned before, we did not notice a qualitative difference in the DOS between the room temperature and the low temperature higher symmetry structures. For both of them the peak at the Fermi level is found. The splitting of the peak when Ba2 atom is shifted toward one of the split positions indicates that the locking of barium atoms might be the most important process at the phase transition. If we assume that at the phase transition this locking of barium atoms occurs then the reduction of the DOS at the Fermi level is in a qualitative agreement with the observed decrease of magnetic susceptibility. The decrease of the value of DOS is found to be around 25 $`eV^1`$ per unit cell which corresponds to a drop of the Pauli susceptibility of $`2.08\times 10^4cm^3/mol`$ per formula unit that agrees in order of magnitude with the observed one. Paschen ; Silke  Moreover, the area of the Fermi surface is reduced because there are less bands crossing the Fermi level, what can also be seen in Fig. 6. As a consequence, electrical conductivity is expected to be lower and this is also in accord with the experimental observation. It should be emphasised that we did not take into account the effect of the disorder of locked barium atoms. However, due to a very short electron mean free path, which is much smaller than the unit cell parameter, as estimated from experiments and a simple free electron model, Silke  the barium disorder effects should not reflect themselves in the transport properties. The same argument may be applied to understand experimental Hall coefficient results, i.e., the electrons might not be able to close the trajectory on the Fermi surface and therefore the Hall coefficient might not be strongly influenced by the phase transition. The absolute value of DOS at the Fermi level is in agreement with the low temperature specific heat measurements.Malte  If we assume the locking of barium atoms at low temperatures and take the corresponding value of DOS of 25 $`eV^1`$ at the Fermi level, we obtain $`\gamma =`$ 15 $`mJ/molK^2`$ per formula unit. The experimental value is 21 $`mJ/molK^2`$ per formula unit. For the Ba4Na2Ge25, discussed in the next section, we obtain 29 $`mJ/molK^2`$ per formula unit in comparison with the experimental 33 $`mJ/molK^2`$ per formula unit. The measurements of the variation of superconducting transition temperature under pressure show that Tc is increased 16 times, from the value of 0.24 K at zero pressure, as the structural phase transition is suppressed. Introducing the values of DOS for higher and lower symmetry structure in the McMillan expression for TcMcMillan  provides the ratio of 21, in a relatively good agreement with the observed one.

### IV.3 The results for Ba4Na2Ge25

The total band structure for Ba4Na2Ge25 is qualitatively similar to that found for Ba6Ge25. The Fermi level is shifted downwards because there are less electrons and the gap between bonding and anti-bonding region is narrower since the lattice parameter is smaller compared to Ba6Ge25. The peak of DOS at the Fermi level is also found.

In order to examine the influence of the sodium on the band structure, we performed a calculation on a fictitious Ba$`{}_{4}{}^{}\mathrm{}_{2}^{}`$Ge25 compound and compare it with Ba4Na2Ge25. The inclusion of sodium atoms introduces a lowering of the bands at the beginning of the conduction band together with the most upper parts of the valence bands, so that the fundamental gap has nearly the same value. The conduction bands are modified. Although some similarities may be observed, rigid-band model could hardly be applied. In the valence region, however, apart from the bands just below the fundamental gap, near $`\mathrm{\Gamma }`$ point, the band structures are almost identical. Introduction of sodium does not influence the bonding states of germanium. The $`l`$-projected DOS in sodium atomic spheres are shown in Fig. 8, and compared with the pertinent empty sphere. In the sodium sphere a peak of mainly $`s`$-symmetry at the Fermi level is found, where the modifications of the band structure, considered above, is observed.

We have also performed a calculation on Ba4Ba2Ge25, where we have inserted barium instead of sodium atoms and kept the same symmetry and the structure. It is interesting that no shifting of the conduction band is observed. However, the band structure undergoes stronger changes than in the case of sodium. Even the valence region, i.e., bonding germanium states, is significantly affected. The $`l`$-projected DOS in the barium spheres, as in Ba6Ge25, discovers the appearance of the states of $`d`$-symmetry (Fig. 8). The large contribution of $`d`$-symmetry states are present around and above the Fermi level, in contrast to the sodium and the empty spheres, where their contribution is small.

The electron charges, projected on the states of particular $`l`$-symmetry, in the sodium, barium, and empty spheres for corresponding compounds are given in the Table 3. Since in the empty spheres only the tails from germanium states are present, the difference to the spheres of sodium and barium should give the contribution of more atomic-like states. In the sodium sphere, the charge is mainly in the states of $`s`$-symmetry, but comparable contributions are found in the states of $`p`$\- and somewhat less in $`d`$-symmetry states. Due to the change of the potential in the sodium sphere in comparison with empty one, it is hard to disentangle the contribution coming from germanium tails. The values, however, indicate hybridisation of sodium $`s`$\- and $`p`$-states with germanium states, although not so strong as in the case of barium in Ba4Ba2Ge25, where a distinctively large contribution of $`d`$-symmetry states in the barium sphere is found, which again points to the strong hybridisation of barium $`d`$-states with germanium $`p`$-states.

A shifting of sodium atoms to one of the split positions did not produce such a splitting of the band structure as in the case of Ba6Ge25, although some reduction of DOS is observed.

## V Summary and conclusion

We have performed LDA band structure calculations for the two clathrates, Ba6Ge25 and Ba4Na2Ge25, using LMTO method within the atomic sphere approximation. The overall band structure reveals similarities with Ge in diamond type structure and the comparison with empty Ge cage shows very similar structure in the bonding region. However, the conduction bands, in particular at the Fermi level, have a strong contribution of barium states. The analysis of the $`l`$-projected DOS shows that these states are of strong $`d`$-symmetry character. The calculations yield the peak of the DOS at the Fermi level that hints on the structural instabilities of the system. In Ba6Ge25, shifting of Ba2 atoms, which have the largest and the most aspherical atomic displacement parameter, toward one of the experimentally deduced split positions splits the peak and reduces the DOS. The splitting of the peak at the Fermi level, due to the shifting of Ba2 atoms and corresponding symmetry lowering, may therefore be considered as the band Jahn-Teller effect. Barium in Ba6Ge25 clathrate can not be considered as the electron donor only and this compound does not fit into the simple concept of PGEC. In the case of Ba4Na2Ge25, the shifting of sodium atoms to one of the split positions does not produce such a pronounced tendency toward splitting the peak of DOS. If the locking of Ba2 atoms in Ba6Ge25 at the phase transition is assumed, the reduction of DOS at the Fermi level is in the agreement with experimentally observed abrupt decrease of the magnetic susceptibility and with the observed variation of superconducting transition temperature with pressure. It may qualitatively account for the observed reduction of the electrical conductivity. The specific heat coefficient $`\gamma `$ obtained from the low temperature specific heat measurements is also in agreement with the calculated value of DOS at the Fermi for Ba6Ge25 with barium atoms locked, and for Ba4Na2Ge25 in the average structure.

###### Acknowledgements.

We wish to acknowledge useful discussions with P. Fulde, S. Paschen, F. M. Grosche and W. Carrillo-Cabrera.


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# Concentration Dependence of the Flory 𝜒 Parameter within Two-State Models

## I Introduction

The Flory free energy plays a central role in the thermodynamics of polymers. In this free energy, the mixing energy term has the form $`\chi \varphi (1\varphi )`$ where $`\chi `$ is the Flory interaction parameter and $`\varphi `$ is the monomer volume fraction. Typically, it is assumed that $`\chi `$ depends only on the temperature, $`\chi =\chi (T)`$.Flory ; PGG ; GK ; Doi  However when thermodynamic data are analyzed in terms of the Flory free energy, it is often necessary to replace $`\chi \varphi (1\varphi )`$ by $`\chi _{eff}\varphi (1\varphi )`$ where $`\chi _{eff}`$ is a function of both $`T`$ and $`\varphi `$ i.e., $`\chi _{eff}=\chi _{eff}(T,\varphi )`$.Flory ; wolf ; Molyneux ; Rowlinson ; nom  Considerable effort was devoted to clarifying the statistical mechanical origins of this and other deviations from the Flory-Huggins theory. Various extensions of the Flory-Huggins theory allow for compressibility,sanchez  local compositionlocalcomp  and the role of intrachain contacts.Painter  Recently, the lattice cluster theory utilized a more accurate solution of the lattice model while allowing for the structure of the monomers.Freed  The Flory-Huggins theory was also extended in order to account for the phase behavior of aqueous solutions of neutral water-soluble polymers and in particular polyetheleneoxide (PEO). In such systems the solubility of the polymers is attributed to the formation of H-bonds. These extensions introduce a two-state model wherein the monomers of the chain can exist in two distinct and interconverting statesGoldstein ; K ; tanaka ; n-Cluster ; BBP  (Figure 1). In the following we demonstrate that “two-state” models yield $`\chi _{eff}(\varphi )`$ and analyze the $`\varphi `$ dependence of the resulting $`\chi _{eff}`$. Our discussion is mostly concerned with two models: The one proposed by Karlstrom (K model)K  and the model of Matsuyama and Tanakatanaka  as formulated by Bekiranov, Bruinsma and Pincus (MB model).BBP

The two models differ, as we shall discuss, in the precise identification of the monomeric states. However, in both cases it is assumed that one monomeric state, $`A`$, is “hydrophilic” while the other, $`B`$, is “hydrophobic”. As a result, a binary solution of a polymer in water behaves in fact as a reactive ternary system. In particular, the fraction of $`A`$ monomers, $`P`$, depends on both $`T`$ and $`\varphi `$. Consequently the different versions of this model yield, as we shall see, $`\chi _{eff}`$ that depends on both $`T`$ and $`\varphi `$. The original papers proposing theses models K ; tanaka ; BBP  focused on the phase behavior while overlooking the emergence of $`\chi _{eff}(\varphi )`$foot .

The goal of our work is to obtain explicit expressions for $`\chi _{eff}(\varphi )`$ for the K and MB models, analyze the $`\varphi `$ dependence and compare the results to experimental data. It is noteworthy that by allowing for the internal degrees of freedom of the monomers, the two-state models can rationalize the observed $`\chi _{eff}(\varphi )`$ while retaining the main approximations of the Flory-Huggins theory i.e., incompressibility, monomers and solvent molecules of identical size and shape and local concentration that equals the global one. Aside from the fundamental interest in the origin of the $`\varphi `$ dependence of $`\chi _{eff}`$ this analysis underlines the utility of $`\chi _{eff}(\varphi )`$ as a criterion for the performance of the models.

While both the K model and the MB model recover the observed phase diagram of PEO, only the K model yields a qualitatively correct $`\chi _{eff}(\varphi )`$. On the other hand, an opposite trend is found for $`\chi _{eff}(\varphi )`$ of polyvinylpiridon (PVP) which exhibits a $`\varphi `$ dependence that differs qualitatively from that of PEO Martien (Figure 2). In this case the K model is inherently incapable of reproducing the experimental results while the MB model does allow for a similar behavior.

Our analysis is mostly concerned with the concentration dependence of

$$\overline{\chi }=\chi _{eff}(1\varphi )\frac{\chi _{eff}}{\varphi }.$$
(1)
We choose to focus on $`\overline{\chi }`$ because measurements of colligative properties, such as vapor pressure and osmotic pressure, yield $`\overline{\chi }`$ rather than $`\chi _{eff}`$.wolf  As a result, it is the $`\overline{\chi }`$ values that are usually reported in the literature. Furthermore, it turns out that the $`\varphi `$ dependence of $`\overline{\chi }(\varphi )`$ is simpler to analyze. Since the different versions of the two-state model aimed to rationalize the phase behavior of aqueous solutions of PEO, the parameters involved were chosen with view of recovering the known phase diagram. However, these models are in fact suitable candidates for the description of aqueous solutions of neutral water-soluble polymers in general. With this in mind we consider the two-state model as a generic model for such systems rather than as a specific model for PEO. Accordingly, we make no specific assumptions regarding the choice of the various parameters involved.

The paper is organized as follows. A unified description of the K and MB models, stressing the similarities and the differences, is presented in section II. Section III contains a brief summary of the thermodynamics of polymer solutions with $`\chi _{eff}(\varphi )`$. This discussion introduces the approach utilized later for the study of $`\overline{\chi }(\varphi )`$. $`\chi _{eff}(\varphi )`$, $`\overline{\chi }(\varphi )`$ and $`\overline{\chi }(\varphi )/\varphi `$ for the K and MB models are discussed in sections IV and V respectively. In the discussion we compare the K and MB models with two other physically transparent models yielding a $`\varphi `$ dependent $`\chi _{eff}`$.

## II Two “two-state” Models

In the “two-state” models for water-soluble homopolymers the monomers of the chain may assume two interconverting forms characterized by different interaction energies. In particular, one monomeric state, $`A`$, is assumed to be “hydrophilic” while the other, $`B`$, is assumed to be “hydrophobic”. The K and MB models differ somewhat with respect to the underlying physics. The K modelK  focuses on molecular rotations giving rise to monomeric states of different polarities. The state endowed with a strong dipole moment is identified as the hydrophilic species, $`A`$, while the less polar state is identified as the hydrophobic state, $`B`$. Within this model the interconversion is a unimolecular reaction, $`AB`$, and the mass action law is

$$\frac{P}{1P}=K_K$$
(2)
Here $`P`$ is the fraction of monomers in a hydrophilic $`A`$ state and $`K_K`$ is the corresponding equilibrium constant. The explicit form of $`K_K`$, to be given in section IV, is irrelevant at this point. The MB modelBBP  focuses on the role of H-bonds. In particular, a monomer that forms H-bond with water is considered, in effect, as hydrophilic while a monomer that does not form such bond is hydrophobic. Within this model one distinguishes between free water molecules ($`S`$) and water molecules that are bound to the polymer chain. This distinction has no counterpart in the K model. Accordingly the interconversion reaction is a bimolecular reaction, $`B+SA`$, and the chemical equilibrium is specified by

$$\frac{P}{(1P)\varphi _0}=K_{MB}$$
(3)
where $`\varphi _0`$ is the volume fraction of water. The explicit expression for $`K_{MB}`$, to be given in section V, is not required for the present discussion. Thus, in the K model

$$\varphi _0=1\varphi $$
(4)
while in the MB model

$$\varphi _0=1\varphi P\varphi $$
(5)
where $`P`$ is the fraction of monomers that form H-bonds and $`P\varphi `$ is the volume fraction of bound water. As a result, the two models involve different reference states. In particular, the melt state, $`\varphi =1`$, in the K model is characterized by

$$P(\varphi =1)=P_{}0$$
(6)
while in the MB model

$$P(\varphi =1)=0$$
(7)
Both models utilize a Flory type approach to obtain the thermodynamics of the solution. In particular, random mixing is assumed and the energy per site of a polymer-water solution inscribed on a lattice is written as

$`{\displaystyle \frac{E}{kT}}=\varphi \left[P{\displaystyle \frac{zϵ_{AA}}{2kT}}+\left(1P\right){\displaystyle \frac{zϵ_{BB}}{2kT}}\right]+(1\varphi ){\displaystyle \frac{zϵ_{SS}}{2kT}}+`$
$`\varphi (1\varphi )\left[P\chi _{AS}+(1P)\chi _{BS}\right]+\varphi ^2\chi _{AB}P(1P),`$ (8)
where $`z`$ is the coordination number of the lattice and $`k`$ is the Boltzmann constant. $`ϵ_{AA}`$, $`ϵ_{BB}`$ and $`ϵ_{SS}`$ denote respectively the energies of $`A`$, $`B`$ and solvent molecules in a pure bulk phase. $`\chi _{AB}`$, $`\chi _{AS}`$ and $`\chi _{BS}`$ denote the Flory interaction parameters corresponding respectively to $`AB,`$ $`AS`$ and $`BS`$ interactions (where $`\chi _{AS}=ϵ_{AS}(ϵ_{AA}+ϵ_{SS})/2`$ etc). The first term allows for the energy of the $`A`$ and $`B`$ in a hypothetical pure bulk phase while the second reflects the energy of the solvent molecules in a pure bulk state. The interactions between the two monomeric states and the solvent gives rise to the third term while the last term allows for the $`AB`$ interactions. For future reference it is convenient to define a dimensionless parameter

$$\mathrm{\Delta }ϵ=z\frac{ϵ_{AA}ϵ_{BB}}{2kT}$$
(9)
characterizing the difference between the energies of the two monomeric states. This expression reduces to the familiar Flory form when $`P=1`$ or $`P=0`$ that is, when the monomers have only one state. The energy $`E`$ is supplemented by two entropy contributions per lattice site. One term allows for the different possible sequences of $`A`$ and $`B`$ states along the chain

$$\frac{S_{AB}}{k}=\varphi \left[P\mathrm{ln}P+(1P)\mathrm{ln}(1P)\right]$$
(10)
while the second reflects the translational entropy of the chains

$$\frac{S_{trans}}{k}=\frac{\varphi }{N}\mathrm{ln}\frac{\varphi }{N}\varphi _0\mathrm{ln}\varphi _0.$$
(11)
The $`S_{AB}`$ term is distinctive to the two-state models. It vanishes when the monomers exist in a single state i.e., $`P=1`$ or $`P=0`$. As expected, $`S_{trans}`$ is identical in form to the entropy term in the Flory free energy. Altogether, the free energy of the solution is $`F=ET(S_{AB}+S_{trans})`$ and the mixing free energy is

$$F_{mix}=F(\varphi ,P)\varphi F(\varphi =1)(1\varphi )F(\varphi =0)$$
(12)
Both models neglect the fluctuations in the number of $`A`$ monomers per chain, $`m`$. Strictly speaking, chains with different $`m`$ are distinguishable and should be treated as different chemical species.tanaka  Rather than allow for this multiplies equilibrium the K and MB models consider a single polymer species characterized by an average $`\overline{m}=PN`$ where $`N`$ is the polymerization degree. This approximation is justified because the $`m`$ values are described by a sharply peaked Gaussian distribution.BBP  While the two models lead to similar free energies, the free energies invoked in the K and in the MB-models differ in two respects. In the MB model (i) The translational entropy is $`P`$ dependent because of the $`\varphi _0\mathrm{ln}\varphi _0`$ term and, (ii) since $`P(\varphi =1)=0`$, $`F_{mix}`$ does not reflect contributions due to $`P(\varphi =1)=P_{}0`$ that appears in the K model.

Finally, it is helpful to note certain additional differences between the models as described in the original papers.K ; BBP  While the physical content of these is minor in comparison to the differences discussed above, they are of interest for comparison purposes. Thus, the analysis of Bekiranov et al focused on the particular case of $`\chi _{AB}=0`$, $`\chi _{AS}=\chi _{BS}=\chi =2.8850.0036T`$ and $`\mathrm{\Delta }ϵ=6.382408/T`$ while in the K model $`\chi _{AS}=80.0/T,\chi _{BS}=684.5/T`$, $`\chi _{AB}=155.6/T`$ and $`\mathrm{\Delta }ϵ=625.2/T+\mathrm{ln}8`$. The temperature dependence of the $`\chi `$ parameters in the two papers is somewhat different. Bekiranov et al assume $`\chi a+bT`$ while in the K model $`\chi b/T`$. In both models $`\mathrm{\Delta }ϵa+b/T`$. In the model of Bekiranov et al this follows from the identification of $`\mathrm{\Delta }ϵ`$ with $`\mathrm{\Delta }F_0/kT`$ where $`\mathrm{\Delta }F_0=\mathrm{\Delta }E_0T\mathrm{\Delta }S_0`$ is the free energy change associated with the formation of H-bond. The $`a+b/T`$ dependence in the K model is a consequence of the degeneracy of the monomeric states. It assumed that each of the two monomeric forms can exist in a number of equivalent states and the resulting entropy gives rise to $`a`$. The analysis of Bekiranov et al allows for the effect of pressure. This is attributed to the existence of a preferred volume for a H-bond.Poole  The application of pressure is assumed to introduces a geometric constraint resulting in a lower number of bound water molecules. This argument yields a semiquantitative agreement with experimental results on the phase diagram of PEO. Note that this coupling mechanism can only operate within the MB model and can not be used in the K model. Furthermore, it is not fully consistent with the incompressibility assumption invoked by Bekiranov et al.

## III Thermodynamics of Polymer Solutions with $`\chi _{eff}(\varphi )`$

Before we proceed to analyze the $`\varphi `$ dependence of $`\overline{\chi }`$ within the two “two-state” models, it is helpful to summarize the thermodynamic relationships that apply when $`\chi =\chi (T)`$ is replaced by $`\chi _{eff}=\chi _{eff}(T,\varphi )`$wolf . The Flory like mixing free energy per site, $`F_{mix}`$, consists then of two terms. One is an interaction free energy that is the counterpart of the mixing energy $`\chi \varphi (1\varphi )`$

$$\frac{F_{int}}{kT}=\chi _{eff}(\varphi )\varphi (1\varphi ).$$
(13)
The second is the translational free energy

$$\frac{F_{trans}}{kT}=\frac{1}{N}\varphi \mathrm{ln}\varphi +(1\varphi )\mathrm{ln}(1\varphi ).$$
(14)
The chemical potential of the solvent is $`\mu _s=\mu _s^o(P,T)\pi a^3`$ while the osmotic pressure $`\pi a^3=\varphi ^2\frac{}{\varphi }(\frac{F_{mix}}{\varphi })`$ is

$$\frac{\pi a^3}{kT}=\frac{\varphi }{N}\varphi \mathrm{ln}(1\varphi )\overline{\chi }\varphi ^2$$
(15)
where $`\overline{\chi }=\chi _{eff}(1\varphi )\frac{\chi _{eff}}{\varphi }`$ replaces $`\chi `$. Since $`\mu _s`$ determines the colligative properties of the solution, measurements of such properties yield $`\overline{\chi }`$ rather than $`\chi _{eff}`$. In turn, $`\overline{\chi }`$ is obtainable from $`F_{int}`$ via

$$\overline{\chi }=\frac{}{\varphi }\frac{F_{int}}{kT\varphi }$$
(16)
In the next two sections we will utilize equation (16) to obtain $`\overline{\chi }`$ from $`F_{int}=F_{mix}F_{trans}`$. This equation also shows that terms of the form $`const^{}\varphi `$ in $`F_{int}`$ do not contribute to $`\overline{\chi }`$. This will allow us to ignore such linear terms that arise because of the choice of the reference state.

## IV $`\overline{\chi }`$ within the K model

Within the K model the mixing energy per lattice site, $`E_{mix}`$, is

$`{\displaystyle \frac{E_{mix}}{kT}}`$ $`=`$ $`\varphi P\mathrm{\Delta }ϵ+\varphi (1\varphi )[P\chi _{AS}+(1P)\chi _{BS}]+`$ (17)
$`\varphi ^2\chi _{AB}P(1P)+\text{terms linear in }\varphi `$
The first term measures the difference in the energy of isolated $`A`$ and $`B`$ monomers. The second term accounts for the interactions between the monomers and the solvent. It is a generalization of the $`\chi \varphi (1\varphi )`$ term in the Flory free energy for a binary solutions. The third term allows for the interaction between $`A`$ and $`B`$ monomers. The mixing entropy is

$`{\displaystyle \frac{S_{mix}}{k}}=\varphi [P\mathrm{ln}P+(1P)\mathrm{ln}(1P)]`$ (18)
$`\left[{\displaystyle \frac{\varphi }{N}}\mathrm{ln}\varphi +(1\varphi )\mathrm{ln}(1\varphi )\right]+\text{terms linear in }\varphi `$
The first term allows for the $`AB`$ mixing within the chains and the second for the translational entropy of the chains. In both expressions, the terms linear in $`\varphi `$ arises because the free energy of the melt state depends on $`P_{}`$ and $`F_{mix}=F(1\varphi )F(\varphi =0)\varphi F(\varphi =1,P_{})`$. Upon discarding terms linear in $`\varphi `$, $`F_{int}=F_{mix}F_{trans}`$ is

$`{\displaystyle \frac{F_{int}}{kT}}=\varphi P\mathrm{\Delta }ϵ+\varphi (1\varphi )[P\chi _{AS}+(1P)\chi _{BS}]+`$
$`\varphi ^2\chi _{AB}P(1P)+\varphi [P\mathrm{ln}P+(1P)\mathrm{ln}(1P)]`$ (19)
The equilibrium value of $`P`$ for a given $`\varphi `$ and $`T`$, $`P_e=P_e(\varphi )`$, is specified by the condition $`F_{int}/P=0`$ leading to

$`{\displaystyle \frac{P_e}{1P_e}}=K_K(\varphi ,P_e,T)=`$ (20)
$`\mathrm{exp}\left[\mathrm{\Delta }ϵ(1\varphi )(\chi _{AS}\chi _{BS})\varphi \chi _{AB}(12P_e)\right]`$
where $`K_K`$ is the equilibrium constant for the unimolecular intrachain $`AB`$ reaction. When $`\chi _{AS}=\chi _{BS}=\chi `$ and $`\chi _{AB}=0`$, the parameters chosen by Bekiranov et. al., $`K_K`$ is independent of $`\varphi `$. Consequently, for this case $`P_e`$ is independent of $`\varphi `$, $`P_e/\varphi =0`$, thus leading, as we shall see, to $`\overline{\chi }_K/\varphi =0`$. To assure the stability of the $`AB`$ equilibrium we further invoke the condition $`^2F_{int}/P^2>0`$

$$\frac{^2F_{int}}{P^2}=\varphi \left[\frac{1}{P(1P)}2\varphi \chi _{AB}\right]>0.$$
(21)
This ensures that the free energy curve is concave and that fluctuation relax back to the equilibrium state according to the LeChatelier principle. Using $`\overline{\chi }=\frac{}{\varphi }\frac{F_{int}}{kT\varphi }`$ and the equilibrium condition we find

$$\overline{\chi }_K=P_e\chi _{AS}+(1P_e)\chi _{BS}\chi _{AB}P_e(1P_e)$$
(22)
Thus, within the K model the $`\varphi `$ dependence of $`\overline{\chi }_K`$ is due to $`P_e(\varphi )`$. In order to specify $`\overline{\chi }_K/\varphi `$ it is first necessary to obtain $`P_e(\varphi )/\varphi `$ by differentiating the equilibrium condition (20) with respect to $`\varphi `$ leading to

$$\frac{P_e(\varphi )}{\varphi }=\frac{\overline{\chi }_K}{P_e}\frac{\varphi }{^2F_{int}/P^2}.$$
(23)
Here, and later in (24), $`^2F_{int}/P^2`$ signifies the value of (21) in equilibrium i.e., $`P=P_e(\varphi )`$. Equation (23) indicates that the sign of $`P_e(\varphi )/\varphi `$ is determined by $`\overline{\chi }_K/P_e`$. This reflects the concentration dependence of $`K_K=const^{}\mathrm{exp}(\varphi \overline{\chi }_K/P_e)`$. Altogether

$$\frac{\overline{\chi }_K}{\varphi }=\frac{\overline{\chi }_K}{P_e}\frac{P_e}{\varphi }=\left(\frac{\overline{\chi }_K}{P_e}\right)^2\frac{\varphi }{^2F_{int}/P^2}0$$
(24)
and $`\overline{\chi }_K`$ is an increasing function $`\varphi `$ for any choice of the parameters $`\chi _{AS}`$, $`\chi _{BS}`$, $`\chi _{AB}`$ and $`\mathrm{\Delta }ϵ`$ except for the case $`\chi _{AS}=\chi _{BS}`$ and $`\chi _{AB}=0`$ when $`\overline{\chi }_K/\varphi =0`$. The calculated $`\overline{\chi }_K(\varphi )`$, utilizing the parameters used to fit the phase diagram of PEO, is in semiquantitative agreement with the experimental results for $`\overline{\chi }(\varphi )`$ (Figure 3). The resulting curve is representative of the behavior of $`\overline{\chi }_K(\varphi )`$ in general.

## V $`\overline{\chi }`$ within the MB model

The mixing energy per site in the MB model is essentially identical to that of the K model

$`{\displaystyle \frac{E_{mix}}{kT}}`$ $`=`$ $`\varphi P\mathrm{\Delta }ϵ+(1\varphi )\varphi \left[P\chi _{AS}+(1P)\chi _{BS}\right]+`$ (25)
$`\varphi ^2\chi _{AB}P(1P)`$
while the mixing entropy per site is

$`{\displaystyle \frac{S_{mix}}{k}}`$ $`=`$ $`\varphi [P\mathrm{ln}P+(1P)\mathrm{ln}(1P)]`$ (26)
$`\left[{\displaystyle \frac{\varphi }{N}}\mathrm{ln}\varphi +(1\varphi P\varphi )\mathrm{ln}(1\varphi P\varphi )\right].`$
These differ from the corresponding expressions within the K model in two respects: (i) Terms linear in $`\varphi `$ are no longer present because the dependence on $`P_{}`$ disappears since $`P(\varphi =1)=0`$ (ii) The translational entropy contribution to $`S_{mix}`$ now depends on $`P`$ because $`\varphi _0=1\varphi P\varphi `$. $`F_{int}=F_{mix}F_{trans}`$ is

$`{\displaystyle \frac{F_{int}}{kT}}=\varphi P\mathrm{\Delta }ϵ+\varphi (1\varphi )[P\chi _{AS}+(1P)\chi _{BS}]+`$
$`\varphi ^2\chi _{AB}P(1P)+\varphi [P\mathrm{ln}P+(1P)\mathrm{ln}(1P)]`$
$`P\varphi \mathrm{ln}(1\varphi )+(1P\varphi \varphi )\mathrm{ln}\left(1{\displaystyle \frac{P\varphi }{1\varphi }}\right).`$ (27)
The equilibrium value of $`P`$, for a given $`\varphi `$ and $`T`$ is specified by the condition $`F_{int}/P=0`$

$`K_{MB}(\varphi ,P_e,T)={\displaystyle \frac{P_e}{(1P_e)(1P_e\varphi \varphi )}}=`$ (28)
$`\mathrm{exp}\left[1\mathrm{\Delta }ϵ(1\varphi )(\chi _{AS}\chi _{BS})\varphi \chi _{AB}(12P_e)\right]`$
where $`K_{MB}=eK_K`$ is the equilibrium constant for the $`B+SA`$ reaction. As in the K model, $`K_{MB}`$ is independent of $`\varphi `$ when $`\chi _{AS}=\chi _{BS}`$ and $`\chi _{AB}=0`$.

However, in the MB model $`P_e`$ depends on $`\varphi `$ even when $`K_{MB}`$ does not because of the loss of translational entropy of the bound water. The stability condition for the $`B+SA`$ reaction, $`^2F_{int}/P^2>0,`$ leads to

$$\frac{^2F_{int}}{P^2}=\varphi \left[\frac{1}{P(1P)}2\varphi \chi _{AB}+\frac{\varphi }{1\varphi P\varphi }\right]>0.$$
(29)
Using $`\overline{\chi }=\frac{}{\varphi }\frac{F_{int}}{kT\varphi }`$ and the equilibrium condition (28) we find

$`\overline{\chi }_{MB}`$ $`=`$ $`P_e\chi _{AS}+(1P_e)\chi _{BS}\chi _{AB}P_e(1P_e)+`$ (30)
$`{\displaystyle \frac{P_e}{\varphi }}+{\displaystyle \frac{1}{\varphi ^2}}\mathrm{ln}\left(1{\displaystyle \frac{P_e\varphi }{1\varphi }}\right).`$
While the first three terms are identical in form to $`\overline{\chi }_K`$ these are now supplemented by two additional terms arising from the translational entropy of the water. When $`\chi _{AS}=\chi _{BS}=\chi `$ and $`\chi _{AB}=0`$ the interaction terms are constant, $`\overline{\chi }_K=\chi `$, and the $`\varphi `$ dependence of $`\overline{\chi }_{MB}`$ reflects solely the entropic contribution. Again we obtain $`P_e(\varphi )/\varphi `$ by differentiating the equilibrium condition, (28), with respect to $`\varphi `$ finding

$$\frac{P_e(\varphi )}{\varphi }=\frac{\overline{\chi }_{MB}}{P_e}\frac{\varphi }{^2F_{int}/P^2}.$$
(31)
In equation (31), and later in (32), $`^2F_{int}/P^2`$ denotes the value of (29) in equilibrium. While equation (31) is similar in form to (23) the two are not identical because the two models yield different $`P_e`$ and because $`\overline{\chi }_{MB}/P_e\overline{\chi }_K/P_e`$. As before the sign of $`P_e(\varphi )/\varphi `$ is determined by $`\overline{\chi }_{MB}/P_e`$. This reflects the concentration dependence of $`K_{MB}^{^{}}=(1\varphi P\varphi )K_{MB}`$ in particular, $`\overline{\chi }_{MB}/P_e=\mathrm{ln}K_{MB}^{^{}}/\varphi `$. Upon substituting $`P_e(\varphi )/\varphi `$ into $`\overline{\chi }_{MB}/\varphi `$ as found from (30) we obtain

$`{\displaystyle \frac{\overline{\chi }_{MB}}{\varphi }}`$ $`=`$ $`\left({\displaystyle \frac{\overline{\chi }_{MB}}{P_e}}\right)^2{\displaystyle \frac{\varphi }{^2F_{int}/P^2}}`$ (32)
$`{\displaystyle \frac{2}{\varphi ^3}}\mathrm{ln}\left(1{\displaystyle \frac{P_e\varphi }{1\varphi }}\right)`$
$`{\displaystyle \frac{P_e}{\varphi ^2}}\left[1+{\displaystyle \frac{1}{(1\varphi )(1P_e\varphi \varphi )}}\right]`$
The first two terms are positive. Of these, the first is analogous to the corresponding result within the K model. The third term is negative. As a result, $`\overline{\chi }_{MB}/\varphi `$ is no longer positive definite. Depending on the choice of $`\chi _{AS}`$, $`\chi _{BS}`$, $`\chi _{AB}`$ and $`\mathrm{\Delta }ϵ`$ the calculated $`\overline{\chi }_{MB}`$ can be monotonically increasing or decreasing as well as exhibit a minimum or a maximum (Figure 4). In the case of PEO the calculated $`\overline{\chi }_{MB}(\varphi )`$, utilizing the parameters used to fit the phase diagram of PEO, differs qualitatively from the experimentally measured $`\overline{\chi }(\varphi )`$ (Figure 5).

## VI Discussion

As we have seen, two versions of the “hydrophobic-hydrophilic” two-state model for water-soluble polymers in aqueous solutions lead to a $`\varphi `$ dependent $`\chi _{eff}`$. The K-version, where the two states undergo unimolecular intrachain conversion, results in $`\overline{\chi }/\varphi >0`$. Using $`\chi _{AS}`$, $`\chi _{BS}`$, $`\chi _{AB}`$ and $`\mathrm{\Delta }ϵ`$ as obtained by fitting the phase diagram of PEO this model yields $`\overline{\chi }`$ that agrees semiquantitatively with the experimentally observed valuesMolyneux ; Rowlinson  (Figure 3). Within the MB model the hydrophilic monomeric state binds a water molecule. As a result, the interconversion reaction is bimolecular and the translational entropy of the water plays a role in determining the equilibrium state. In this model $`\overline{\chi }`$ can display a number of scenarios (Figure 4): $`\overline{\chi }(\varphi )`$ can be monotonically increasing, monotonically decreasing or exhibit an extremum (maximum or minimum).

The $`\overline{\chi }`$ vs. $`\varphi `$ as calculated with the parameters used to fit the phase diagram of PEO, differs qualitatively from the experimentally obtained curve(Figure 5). However, the $`\overline{\chi }/\varphi <0`$ behavior allowed by this model is of interest since it has been observed in aqueous solutions of the neutral water-soluble polymer PVPMartien  (Figure 2). These results stress the importance of using the experimental values of $`\overline{\chi }`$ in fitting $`\chi _{AS}`$, $`\chi _{BS}`$, $`\chi _{AB}`$ and $`\mathrm{\Delta }ϵ`$ and in evaluating the performance of the model. From the perspective of the general theory of polymers it is of interest that the “two-state” models can account for the dependence of $`\chi _{eff}`$ on $`\varphi `$, $`T`$ and the pressure while retaining the principal approximations of the Flory-Huggins theory i.e., incompressibility, monomer and solvent of identical size and shape and local composition that equals the global one.

At this point it is helpful to consider alternative mechanisms leading to $`\chi _{eff}(\varphi )`$. For brevity we limit this discussion to two physically transparent models. One is the $`n`$-cluster model proposed by de Gennes for aqueous solutions of PEO.n-Cluster  This model was motivated by two experimental observations concerning the behavior of such solutions: (i) the interpretation of calorimetric measurements in terms of the Flory mixing free energy yields a $`\overline{\chi }`$ that increases strongly with $`\varphi `$,Molyneux  and (ii) reports of formation of aggregates in concentrated solutions of PEO.Burchard  Within this model the concentration dependence of $`\chi _{eff}`$ is attributed to attractive interactions leading to stable clusters of $`n>2`$ monomers while binary monomer-monomer interactions remain repulsive. This is another variation of a two-state model involving a dynamic equilibrium between “clustered” and “unclustered” monomers. In molecular terms, a $`n`$-cluster may correspond to a micelle or a mixed helix. The formation of the $`n`$-clusters gives rise to an additional term, $`\rho (T)\varphi ^n`$ (with $`\rho >0`$), in the interaction free energy. Thus, the mixing free energy per site is

$`{\displaystyle \frac{F_{mix}}{kT}}`$ $`=`$ $`\chi \varphi (1\varphi )+\rho (T)(\varphi \varphi ^n)+`$ (33)
$`{\displaystyle \frac{\varphi }{N}}\mathrm{ln}\varphi +(1\varphi )\mathrm{ln}(1\varphi )`$
leading to

$$\chi _{eff}=\chi +\rho \frac{1\varphi ^{n1}}{1\varphi }.$$
(34)
The corresponding $`\overline{\chi }`$ is

$$\overline{\chi }=\chi +\rho (n1)\varphi ^{n2}$$
(35)
and $`\overline{\chi }/\varphi >0`$. The $`n`$-cluster model is indeed capable of rationalizing the two experimental observations noted above. However of these, the second observation is now a subject of debate.antiB  Furthermore the molecular structure of the ethylenoxide monomers does not reveal amphiphilic motifs. It is thus difficult to justify the assumption of cluster formation in solutions of PEO. Accordingly, the validity of this model in the case of aqueous solutions of neutral water soluble polymers such as PEO is not obvious. On the other hand, the model is indeed applicable to solutions of polysoaps where formation of inter and intrachain micelles does occurPolysoaps . The second model, advanced by Painter et al, is applicable to all polymer solutions.Painter  Within this model, the $`\varphi `$ dependence of $`\chi _{eff}`$ is attributed to the interplay of intrachain and interchain contacts. The authors argue that there is a probability $`\gamma `$ for intrachain monomer-monomer contacts. As a rough approximation, $`\gamma `$ can be identified with the monomeric volume fraction, $`\varphi _G`$, within a Gaussian coil of radius $`R_GN^{1/2}a`$ where $`N`$ is the polymerization degree and $`a`$ is the monomer size, $`\varphi _GNa^3/R_0^3N^{1/2}`$. In a lattice comprising of $`N_T`$ sites of coordination number $`z`$ there are $`N_T\varphi `$ sites occupied by monomers with a total of $`N_Tz\varphi `$ adjacent sites. Of the $`N_Tz\varphi `$ adjacent sites $`N_Tz\varphi \gamma `$ are occupied by monomers because of intrachain contacts. The total number of free, unblocked adjacent sites is thus $`N_Tz(1\varphi \gamma )`$ while the number of free sites adjacent to monomers is $`N_Tz\varphi (1\gamma )`$. The probability of a free site adjacent to a monomer is thus $`\varphi (1\gamma )/(1\varphi \gamma ).`$ Accordingly, the number of monomer-solvent contacts is $`N_T(1\varphi )\varphi (1\gamma )/(1\varphi \gamma )`$. This expression allows for the requirement that a solvent molecule occupies an unblocked site adjacent to a monomer. Accordingly, the mixing energy term per site is $`E_{mix}/kT=\chi (1\varphi )\varphi (1\gamma )/(1\varphi \gamma )`$ yielding an enthalpic contribution to $`\chi _{eff}`$

$$\chi _{eff}=\chi \frac{1\gamma }{1\varphi \gamma }$$
(36)
and to a corresponding enthalpic $`\overline{\chi }`$

$$\overline{\chi }=\chi \left(\frac{1\gamma }{1\varphi \gamma }\right)^2$$
(37)
where, again, $`\overline{\chi }/\varphi >0.`$ In their original paper, Painter et al supplemented this enthalpic $`\overline{\chi }`$ by an entropic one, allowing for the effect of the chain bending back on itself following the analysis of Huggins.Huggins

Aside from physical insight regarding the molecular origins of $`\chi _{eff}(\varphi )`$, the above discussion identifies certain difficulties. Overall, it seems unlikely that one of the four models described above will emerge fully victorious. By construction, the $`n`$-cluster model is applicable only to solutions of associating polymers. The two “two-state” models are suitable candidates for the description of aqueous solutions of neutral water-soluble polymers exhibiting insolubility gap. While the model of Painter et al applies, in principle, to all polymeric systems it can not account for systems exhibiting $`\overline{\chi }/\varphi <0`$. Such behavior was actually observed in both aqueous and non-aqueous solutions, yet of the four models considered above only the MB model yields a scenario involving $`\overline{\chi }/\varphi <0`$. Altogether one can thus envision situations where all the different mechanisms described may contribute simultaneously. Another discouraging observation concerns the number of parameters involved. All four models introduce additional parameters that do not appear in the familiar Flory-Huggins theory: $`\gamma `$ in the model of Painter et al, $`\rho `$ and $`n`$ in the $`n`$-cluster model, $`\mathrm{\Delta }ϵ`$, $`\chi _{AB}`$, $`\chi _{AS}`$ and $`\chi _{BS}`$ for the two “two-state” models. The necessity to unambiguously determine the additional parameters limits the predictive power of the models. Clearly, this problem is even more serious when a number of mechanisms contribute simultaneously to the $`\varphi `$ dependence of $`\chi _{eff}`$. Note however that this last difficulty can be partially resolved in certain cases. Thus the contribution of the mechanism of Painter et al can be separated from the one due to the “two-state” mechanism. This is because the mechanism of Painter et al is inherently a polymeric effect that disappears in the monomeric limit, $`N=1`$. On the other hand, the two-state models also apply to solution of the unpolymerized monomers i.e., $`\chi _{eff}`$ and $`\overline{\chi }`$ are independent of $`N`$.

Following our discussion of alternative models for $`\chi _{eff}(\varphi )`$ it is helpful to summarize the evidence favoring the two-state models. Using these models it was possible to derive the phase diagram of PEOK ; BBP  and its pressure dependence.BBP  In addition, the K model was successfully utilized to rationalize a variety of systems involving PEO, Polypropyleneoxyde (PPO)and PEO-PPO copolymers.swedes  These successes lend support to the validity of the two-state model. On the negative side, there is relatively little direct evidence for the existence of the two monomeric states. Computational studies lend the most direct support to the two-state models. The K model is supported by recent molecular dynamics study that monitored the population of hydrophilic and hydrophobic conformations as a function of temperature and concentration and relates their relative stability to polar interactions.Smith  This study utilized force fields obtained from quantum mechanical calculations of dimethoxyethane.Smith1  Somewhat different conclusions were reached in studies of higher oligo(ethylene oxides).WKG  In particular, these studies (i) support the MB model (ii) stress the importance of conformers allowing formation of “water bridges” i.e., where a single water molecule forms two hydrogen bonds with the oxygens in the oligo(ethylene oxides). One such conformer, though not the most stable, is helical. (iii) allow to rationalize force measurements of PEOORG  and, in particular, the difference in the extension force laws found in water and in non- aqueous solvent.KWG  Thus while a consensus on the computational results is yet to emerge, this approach may eventually allow to identify the relevant monomeric states and to obtain $`\mathrm{\Delta }ϵ`$, $`\chi _{AB}`$, $`\chi _{AS}`$ and $`\chi _{BS}`$.


text:
# Weierstraß11footnote 1The last letter is not a 𝛽, but an “ß”, a letter unique to the German alphabet, which is pronounced like an “s”.

Each university and each department, I guess, develops a peculiar kind of folklore: anecdotes about those of its graduates (or dropouts) that somehow managed to become famous (or notorious). Very often, there is an element of glee to these stories: “Well, he may now be a government minister, but I flunked him in calculus!” And also very often, it is impossible to tell truth from legend.

When I was a math student at Münster, Germany, in the 1980s, such anecdotes centered mainly around two people: Gerd Faltings, the first and only German to win the Fields medal, mathematics’ equivalent of the Nobel prize, and Karl Weierstraß222Books written in English usually spell the name “Weierstrass”., the man who (besides many other mathematical accomplishments) introduced $`ϵ`$s and $`\delta `$s into calculus. Weierstraß had been a student at Münster in the 1830s and 1840s. There was no one around anymore who knew anybody who had known anybody who had known anybody who had known Weierstraß. But this didn’t prevent the folklore from blooming. According to folklore, Weierstraß flunked out of law school (because he spent most of his time there drinking beer and doing mathematics); then he worked for more then ten years as a school teacher in remote parts of Prussia, teaching not only mathematics, but also subjects like botany, calligraphy, and physical education. Finally, almost 40 years old, he became a famous mathematician over night, and eventually he was appointed as professor at Berlin — without ever having received a PhD.

This may sound wild, and in some points it simplifies the facts, but it is not far from the truth.

Karl Theodor Wilhelm Weierstraß was born October 31, 1815, in the village of Ostenfelde in what was then the Prussian province of Westphalia. A street and an elementary school in Ostenfelde are named after him, and his birth house — still occupied today — is listed in a local tourist guide. His father, who worked for for Prussia’s customs and taxation authorities, was sent from one post to the next within short periods of time. For the first fourteen years of Karl Weierstraß’ life, the family was more or less constantly on the move. In 1829, the father obtained an assistant’s position at the tax office in the city of Paderborn (also in Westphalia), and the family could finally settle down. Young Karl enrolled at the local Catholic Gymnasium in Paderborn, where he excelled not only in mathematics, but also in German, Latin, and Greek. Not only was he an academically strong student — he was also quite capable of putting his brains to work on much more practical matters: At age 15, he contributed to his family’s income by doing the bookkeeping for a wealthy merchant’s widow.

Throughout his life, Weierstraß senior suffered from the fact that he did not have the right education to rise to a rank in the Prussian civil service that would have really suited his abilities. He had to content himself with relatively low level positions, not very challenging and not very well paid. Like many a father in this situation, he was determined to prevent such a fate for his bright, eldest son. When Karl graduated in 1834, his father decided to send him to Bonn to study Kameralistik, i.e. a combination of law, finance, and administration. Being a dutiful son, Karl went…

…and did all he could to screw up the life his father had planned for him. He joined a schlagende Verbindung, a particular kind of student fraternity typical of German universities in the nineteenth century. Besides keeping the brewing industry busy, students in such a fraternity engaged in a peculiar ritual: the Mensur, a swordfight with a particular twist. Unlike in today’s athletic competitions, the students fought with sharp sabers. They wore protective gear which covered most of their bodies — except the cheeks. During a Mensur, the opponents tried to inflict ghashes on one another’s cheeks. The scars resulting from these ghashes were borne with pride as signs of honor and manhood333If you find such ideas of honor and manhood absolutely revolting, you’re absolutely right.. Almost two meters tall, quick on his feet, and with strong arms, Karl Weierstraß was a fearsome swordsman. His face remained unscarred, and after a while nobody was keen on challenging him anymore. Having escaped from under his father’s tutelage, he spent his years at Bonn drinking beer and wielding the saber — and seriously studying mathematics. Although he was not enrolled in mathematics, he read some of the most advanced math books of his time. When it was time for him, in 1838, to take his exams, he simply dropped out.

His family was desperate. They had made considerable financial sacrifices to secure a better future for Karl, who had let them down. Having wasted four years of his life, he needed a breadwinning degree — and that fast. So, in 1839, he enrolled at the Akademie, a forerunner of today’s university, in Münster to become a secondary school teacher. Although this was not really a university, but rather a teacher training college, they had one good mathematician teaching there: Christoph Gudermann. He is said to have been an abysmal teacher: Very often, he had just one student sitting in his class — Karl Weierstraß. In 1840, Weierstraß graduated. His thesis was so good that Gudermann believed it to be strong enough for a doctoral degree. However, the Akademie was not really a university: It did not have the right to grant doctorates. So, instead of receiving a doctorate and starting an academic career, Weierstraß left the Akademie as a mere school teacher.

His first job (probationary) was in Münster. One year later, he was sent to Deutsch Krona444Now Watcz in Poland. in the provice of West Prussia as an auxiliary teacher and in 1848 to Braunsberg555Now Braniewn in Poland. in East Prussia. Of course, he taught mathematics, but also physics, geography, history, German, and — believe it or not — calligraphy and physical education. Besides the demands of working full time as a teacher and having a social life — remember: he liked beer —, he found time to do research in mathematics. During his time in Braunsberg, he published a few papers in his school’s yearbook. High school year books are not exactly the place where people are looking for cutting edge research in mathematics, and so, nobody noticed them. Then, in 1854, he published a paper entitled “Zur Theorie der Abelschen Functionen” in a widely respected journal. I won’t even make an attempt to explain what it was about. But unlike his previous work, this one was noticed.

It dawned to mathematicians all over Europe that the man who was probably the leading analyst of his day was rotting in a small East Prussian town, spending most of his time teaching youngsters calligraphy and physical education. On March 31, 1854, Weierstraß finally received a doctorate: an honorary one from the university of Königsberg666Now Kaliningrad in Russia., but nevertheless. In 1856, he accepted a position at the Gewerbeinstitut, an engineering school, and a year later he joined the faculty of the university of Berlin as an adjunct professor. As a teacher, he attracted large audiences. Often, he taught in front of more than 200 students. Finally, in 1860, when he was almost 50 years old, Weierstraß was appointed full professor at the university of Berlin. In the years 1873 and 1874, he was Rektor magnificus of the university; in 1875, he became a knight of the order “Pour le Mérite” in the category of arts and sciences, the highest honor newly unified Germany could bestow upon one of her citizens; and in 1885, on the occasion of his 70th birthday, a commemorative coin was issued.

The years of leading a double life as a secondary school teacher and a mathematical researcher had taken their toll on Weierstraß’ health. A less vigorous man would probably have collapsed under the double burden after a short time only. From 1850 on, he began to suffer from attacks of dizziness which culminated in a collapse in 1861. He had to pause for a year before he could teach again, and he never recovered fully. In 1890, — at age 75! — he retired from teaching because of his failing health. The last years of his life, he spent in a wheelchair. In 1897, he died.

Weierstraß published few papers — he was very critical towards his own work. But although, he was a brilliant researcher, the greatest impact he had on mathematics was as a teacher. At Berlin he repatedly taught a two-year course on analysis — the ancestor of all modern introductions to calculus and analysis. Although he never wrote a textbook, notes taken in class by his students have survived and convey an impression of his lectures. The perhaps longest lasting legacy of these lectures is their ephasis on rigor. When calculus was created in the 17th century, mathematicians did not worry about rigorously proving their results. For example, the first derivative $`dy/dx`$ of a function $`y=f(x)`$ was thought of as a quotient of two “infinitesimal”, i.e. infintely small, quantities $`dy`$ and $`dx`$. Nobody could really tell what infinitely small quantities were supposed to be, but mathematicians back then didn’t really care. The new mathematics enabled them to solve problems in physics and engineering which had been beyond the reach of human mind before. So why bother with rigor? In the 18th century, mathematicians went so far as to proclaim that rigor was for philosophers and theologians — not for mathematicians. But with the lack of rigor, contradictory results cropped up with disturbing frequency, i.e. people arrived at formulae that were obviously wrong. And if a particular formulae determines whether or not a bridge collapses, you don’t want it to be wrong. Weierstraß realized that, if calculus was to rest on solid foundations, its central notion, that of limit, had to be made rigorous. He introduced the definition which (essentially) is still used today in classes:

> A number $`y_0`$ is the limit of a function $`f(x)`$ as $`x`$ tends to $`x_0`$ if, for each $`ϵ>0`$, there is $`\delta >0`$ such that $`|f(x)y_0|<ϵ`$ for each $`x`$ with $`|xx_0|<\delta `$.

Students may curse it, but it will not go away.

Weierstraß was not only an influential lecturer, but also one of the most prolific advisors of PhD theses of all time. There is a database on the internet777The Mathematics Genealogy Project at http://hcoonce.math.mankato.msus.edu/. which lists 31 PhD students of Weierstraß and 1346 descendants, i.e. PhDs of PhDs of PhDs of etc. of Weierstraß. Interestingly, the two of his former students who generated the most folklore weren’t his students in a technical sense.

Sofya Kovalevskaya was a young Russian noble woman who had come to Germany to study mathematics. This alone was not a small feat at a time when the very idea of a woman receiving a university education was revolutionary. For two years, she studied at Heidelberg, where authorities would not let her enroll officially, but eventually allowed her to attend lectures unofficially (provided the instructor did not object). Then she moved to Berlin to work with Weierstraß — only to find that there she was not even allowed to sit in lectures. This prompted Weierstraß, by all we know a politically conservative man, to tutor her privately. Since Kovalevskaya could not receive a doctorate from Berlin, Weierstraß used his influence to persuade the university of Göttingen to award her the degree in 1874. The following nine years, she spent jobhunting. Being a woman didn’t help. The best job she could get was teaching arithmetic at an elementary school. Finally, in 1883, she was offered a professorship at Stockholm, where she worked until her death in 1891 at the age of 41. Weierstraß and Kovalevskaya stayed in touch throughout her mathematical career. After her death, Weierstraß destroyed their correspondence. This fact, along with Kovalevskaya’s striking beauty, gave rise to innuedo that she may have been more to Weierstraß, who never married, than just a student. May have been — but we don’t know. This kind of “folklore” probably tells more about those who spread it than about those it is supposedly about.

Gösta Mittag-Leffler also was not strictly speaking Weierstraß’ student. Already being enrolled at the university of Uppsala, Sweden, he came to Berlin in 1875 to attend Weierstraß’ lectures, which turned out to have an enormous impact on his mathematical development. He then returned to his native Sweden, where he received his doctorate. Over the years, he became the undisputedly most influential mathematician of his time in Sweden. He made use of his clout to overcome the obstacles faced by Sofya Kovalevskaya in connection with her appointment at Stockholm. What Mittag-Leffler is most famous for, however, is not a mathematical accomplishment, but a piece of mathematical folklore. To this day, mathematicians suffer quietly from the lack of a Nobel prize in mathematics, and some say, Mittag-Leffler is to blame: According to legend, the first version of Nobel’s will mentioned a prize in mathematics. Then, Nobel found out that his wife had an affair with Mittag-Leffler. Infuriated by the prospect that his wife’s lover could well be the first prize winner, Nobel changed his will and removed the math prize. That’s a fine piece of juicy folklore — but nothing more: Like Weierstraß, Nobel was a lifelong bachelor.

| Address: | Department of Mathematical and Statistical Sciences |
| --- | --- |
|  | University of Alberta |
|  | Edmonton, Alberta |
|  | Canada T6G 2G1 |
| E-mail: | vrunde@ualberta.ca |
| URL: | http://www.math.ualberta.ca/runde/runde.html |


text:
# Hidden symmetries in deformed microwave resonators

\[

## Abstract

We explain the “Hidden symmetries” observed in wavefunctions of deformed microwave resonators in recent experiments. We also predict that other such symmetries can be seen in microwave resonators.

\]

Lauber et al  experimentally studied the pattern of Berry phases that emerges when a microwave cavity is cyclically deformed around a rectangular shape. Standing electromagnetic waves in the cavity can be mapped and the “wave functions” followed through the cyclic deformation to measure the Berry phase. Apart from the Berry phases, which were primarily of interest in ref, those authors also noticed a curious symmetry: the standing wave patterns at different deformations are related. Subsequent theoretical work  has clarified the pattern of Berry phases seen in the experiment. However, the “hidden symmetry” has not been explained so far. The purpose of this brief report is to provide an understanding of the “hidden symmetry” and thus a complete and correct interpretation of the experiment described in .

Consider a rectangular cavity (see Fig.1) with sides $`(a,b)`$ having $`n`$ degenerate modes: the scalar Laplacian $`^2`$ has $`n`$ degenerate eigenfunctions. If the cavity is deformed, the degeneracy will in general be broken. Let us suppose that the deformation consists (as in the experiment of ref. ) of moving the corner around its undeformed position so that the rectangle is deformed to a quadrilateral.     FIG. 1.:  A deformation of a rectangle into a quadrilateral. The vertex $`V=(a,b)`$ is moved to the point $`P=V+(\delta x,\delta y)=V+ab(\alpha ,\beta )`$. We consider an experiment where $`P`$ is moved around the elliptic path shown in the figure.   This deformation can be effected in the formalism by performing a co-ordinate transformation $`x=u(1+\alpha v),y=v(1+\beta u)`$, (where $`(\alpha ,\beta )`$ are the deformation parameters) which maps the deformed rectangle in the $`(x,y)`$ plane to an undeformed rectangle in the $`(u,v)`$ plane. Transforming the Laplacian to curvilinear $`(u,v)`$ coordinates, we find $`H=^2=\frac{1}{\sqrt{g}}\frac{}{x^\mu }\sqrt{g}g^{\mu \nu }\frac{}{x^\nu }`$. Matrix elements of $`H`$ have the form $`<\psi _1|H|\psi _2>=d^2x\sqrt{g}\psi _1^{}^2\psi _2=d^2x\psi _1^{}\frac{}{x^\mu }\sqrt{g}g^{\mu \nu }\frac{}{x^\nu }\psi _2`$. Expanding to first order in $`\alpha ,\beta `$, we then get $`H=H_0+H_1`$, where $`H_0=(_u_u+_v_v)`$ and $`H_1=\alpha f+\beta g`$, with $`f=vX+uY`$, and $`g=uX+vY`$, expressed in terms of the differential operators $`X=_u_u_v_v`$ and $`Y=2_u_v`$.

The unperturbed Hamiltonian $`H_0`$ has the discrete symmetries $`P_1:uau,P_2:vbv`$, the mirror planes of the rectangular box. We now restrict attention to the $`n`$ dimensional degenerate subspace $`_n`$ of $`H_0`$ and choose eigenstates of $`H_0`$ to have definite parity with respect to both these reflections. In fact, we choose these in the form $`|i>=|n_im_i>=(2/\sqrt{ab})\mathrm{sin}\frac{n_iu\pi }{a}\mathrm{sin}\frac{m_iv\pi }{b}`$, where $`n_i,m_i`$ are positive integers. Since the states are all degenerate eigenstates of $`H_0`$, we have $`\frac{n_i^2}{a^2}+\frac{m_i^2}{b^2}=\frac{n_j^2}{a^2}+\frac{m_j^2}{b^2}`$ for all $`i,j`$. In particular $`n_i=n_jm_i=m_j`$. These states are also eigenstates of $`X`$ with eigenvalues $`\lambda _i=(\frac{n_i^2\pi ^2}{a^2}\frac{m_i^2\pi ^2}{b^2})`$. It follows that $`<i|vX|j>=\lambda _j<i|v|j>=\lambda _j<n_i|n_j><m_i|v|m_j>=\lambda _i\delta _{ij}<m_i|v|m_i>`$. From $`P_2vP_2=(bv)`$, it follows that $`<m_i|v|m_i>=<m_i|P_2vP_2|m_i>=b<m_i|m_i><m_i|v|m_i>`$. So we conclude that $`<m_i|v|m_i>=b/2`$ and so, in $`_n`$, $`vX=bX/2`$ and similarly that $`uX=aX/2`$. The form of the perturbations is thus $`f=bX/2+uY,g=aX/2+vY`$.

The “mirror symmetry” observed by Lauber et al in their experiment is related to the way the unperturbed levels transform under parity. We consider all possible cases and thus find the necessary and sufficient conditions for this symmetry to be observed. Let us introduce $`\sigma _{1i}`$ as the $`P_1`$ parity of the ith state ($`P_1|i>=\sigma _{1i}|i>`$) and similarly $`\sigma _{2i}`$ as the $`P_2`$ parity of the ith state. The different cases are listed below with an example (for $`n=3`$) illustrating each non trivial case:

1. $`\sigma _{1i}=\sigma `$ and $`\sigma _{2i}=\sigma ^{}`$ for all $`i=1,2,\mathrm{}n`$ where $`\sigma ,\sigma ^{}`$ can take values $`\pm 1`$ \[Example: $`a=\sqrt{3},b=1`$ and levels $`(2,6),(8,4),(10,2)`$\]. In this case $`<i|uY|j>=<i|P_2(P_2uYP_2)P_2|j>=<i|uY|j>=0`$ and similarly $`<i|vY|j>=<i|P_1(P_1vYP_1)P_1|j>=<i|vY|j>=0`$. Thus $`f=bX/2`$ and $`g=aX/2`$ and this is an uninteresting case because the perturbations do not span a two dimensional space.
2. The product $`\sigma _{1i}\sigma _{2i}=\sigma `$ for all $`i`$, but $`\sigma _{1i}`$ and $`\sigma _{2i}`$ are not the same for all $`i`$ \[Example: $`a=\sqrt{3},b=1`$ and levels $`(1,3),(4,2),(5,1)`$\]. In this case $`<i|uY|j>=<i|P_2P_1(P_1P_2uYP_2P_1)P_1P_2|j>=<i|(au)Y|j>`$ which implies $`uY=aY/2`$. Also $`<i|vY|j>=<i|P_2P_1(P_1P_2vYP_2P_1)P_1P_2|j>=<i|(bv)Yj>`$ and this gives $`vY=bY/2`$. Thus in this case $`f=bX/2+aY/2`$ and $`g=aX/2+bY/2`$. Defining new coordinates: $`\alpha =b\alpha ^{}+a\beta ^{};\beta =a\alpha ^{}+b\beta ^{}`$ we have $`H_1=\alpha f+\beta g=\alpha ^{}(bfag)+\beta ^{}(af+bg)=(a^2+b^2)(\alpha ^{}X/2+\beta ^{}Y/2)`$. Since $`PXP=X,PYP=Y`$ for $`P=P_1,P_2`$, hence we see that wavefunctions at points $`p(\alpha ^{},\beta ^{})`$ and $`p^{}(\alpha ^{},\beta ^{})`$ can be related either by $`P_1`$ or $`P_2`$. Proof: Let $`H_p|\psi _p>=e|\psi _p>`$. Then $`P_1H_{1p}P_1P_1|\psi _p>=eP_1|\psi _p>`$ or $`H_{1p^{}}P_1|\psi _p>=eP_1|\psi _p>`$ which implies, assuming all degeneracies have been lifted, that $`|\psi _p^{}>=\pm P_1|\psi _p>`$. This is the case studied by Lauber et al . Note that the $`\beta ^{}`$ axis is along the long diagonal of the rectangular cavity.
3. $`\sigma _{1i}=\sigma `$ for all $`i`$, but $`\sigma _{2i}`$ is not the same for all $`i`$ \[Example: $`a=2,b=1`$ and levels $`(2,18),(12,17),(20,15)`$\]. In this case $`f=bX/2+uY`$ and $`g=aX/2`$. The coordinate transformation $`\alpha =a\beta ^{};\beta =\alpha ^{}+b\beta ^{}`$ gives $`H_1=\alpha f+\beta g=\alpha ^{}g+\beta ^{}(af+bg)=\alpha ^{}aX/2+\beta ^{}auY`$. Since $`P_2XP_2=X`$ and $`P_2uYP_2=uY`$, it follows that wavefunctions at points $`p(\alpha ^{},\beta ^{})`$ and $`p^{}(\alpha ^{},\beta ^{})`$ can be related by $`P_2`$.
4. $`\sigma _{2i}=\sigma `$ for all $`i`$, but $`\sigma _{1i}`$ is not the same for all $`i`$. This case is similar to (3).
5. Neither of $`\sigma _{1i},\sigma _{2i},\sigma _{1i}\sigma _{2i}`$ is the same for all $`i`$. It can be proved that this case cannot be realized for any choice of $`a,b,n_i,m_i`$. Proof: We enumerate all the possibilities. We can have $`n_i^2/a^2+m_i^2/b^2=n_j^2/a^2+m_j^2/b^2`$ only if $`b^2/a^2`$ is rational. Let $`b^2/a^2=p/q`$, where $`p`$ and $`q`$ are relatively prime. We find that $`n_i^2p+m_i^2q=n_j^2p+m_j^2q=N`$ for all $`i,j`$. Thus we need to consider the following cases classifed according to the parity (odd or even) of $`(p,q)`$ (a) $`(o,o)`$ (b) $`(o,e)`$, (c) $`(e,o)`$, where $`o`$ and $`e`$ denote odd and even parities respectively. For case (a): if $`N`$ is even then the states can have parities $`(P_1,P_2)`$ either $`(,)`$ or $`(+,+)`$. If $`N`$ is odd then they can have parity $`(+,)`$ or $`(,+)`$. Thus the only combinations we can get belong to type (1) or (2). For case (b): if $`N`$ is even then the states can have parity $`(+,+)`$ or $`(+,)`$. If $`N`$ is odd then they can have parity $`(,+)`$ or $`(,)`$. In this case the possible combinations belong to type (3). The case (c) leads to type (3).

Thus there are no examples of type (5).

In summary, we have explained the mirror symmetry of  in the framework of first order perturbation theory (see  for the limitations of this theory) and noticed other situations where such symmetry may be observed.