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# LONGITUDINAL FIELD INFLUENCE ON THE PHASE TRANSITION AND PHYSICAL PROPERTIES OF THE KH2PO4 FAMILY FERROELECTRICS

## 1 Introduction

Studies of ferroelectric crystals behavior under different external factors such as pressure or electric field provide an important information about the phase transition mechanisms in these crystals as well as of their dielectric and piezoelectric responses. Thus, studies of the transition temperature dependence on the geometry of a hydrogen bond revealed a universal dependence of the transition temperature on the distance between equilibrium proton (deuteron) positions on a bond in several crystals of the KH2PO4 family . Studies of the effects produced by external fields conjugate to the order parameter (shear stress $`\sigma _6`$ and electric field $`E_3`$ in these crystals) permit to elucidate the role of structural changes occurring at the phase transition, such as appearance of the shear strain $`\epsilon _6`$.

In our recent paper  we modified the proton ordering model for deuterated KD2PO4 type crystals so that the shear strain $`\epsilon _6`$ was taken into account. We obtained a fair agreement of the theoretical results for associated with strain $`\epsilon _6`$ dielectric, elastic, and piezoelectric characteristics of KD2PO4 (piezoelectric constants $`d_{36}`$, $`e_{36}`$, $`h_{36}`$, $`g_{36}`$, elastic constants $`c_{66}^P`$, $`c_{66}^E`$ and compliances $`s_{66}^P`$, $`s_{66}^E`$, and dielectric permittivity $`\epsilon _{33}`$) with the relevant experimental data.

A consistent taking into account of the changes caused by the strain $`\epsilon _6`$ in the system symmetry revealed that this strain splits the energies of short-range deuteron configurations. Thus, the lowest level of the so-called up and down configurations and the energies of lateral and single-ionized configurations are split. Splitting of up/down and ionized configurations gives rise to single- and three-particle spin terms in the short-range Hamiltonian. Our numerical calculations have shown that by fitting to experimental data one is not able to determine the magnitude of the splitting of up/down configurations $`\delta _{s6}`$, since if a certain ratio between $`\delta _{s6}`$ and the magnitude of piezoelectric internal field $`\psi _6`$ , the experiment is well described in a rather wide range of $`\delta _{s6}`$. A good agreement with the experimental data for temperature behavior of the above mentioned physical characteristics of KD2PO4 is also obtained in a simplified version of the model , where we neglected splitting of the up/down and ionized configurations and took into account only splitting of lateral configurations and piezoelectric internal fields.

In  we show that the transition temperature of KD2PO4 type crystals is increased by the stress $`\sigma _6`$, and the jumps of the order parameter are decreased. At the constructed phase diagram there are two critical points where the phase equilibrium curves terminate. Stresses above critical smear off the phase transition and lead to smooth temperature dependences of polarization and strain. Correspondingly, the peak values of those characteristics of the crystal that have peculiarities at the transition points (the longitudinal dielectric permittivity, compliance $`s_{66}^E`$, piezomodules $`d_{36}`$ and $`e_{36}`$, and specific heat) increase with stress. These peaks are the highest at the critical stress, whereas at stresses above critical their temperature curves are smooth. Such a behavior is peculiar to the ferroelectrics with the first order phase transition in external fields conjugate to the order parameter.

Studies of the stress $`\sigma _6`$ influence on the KH2PO4 family crystals, though interesting they are, remain quite abstract, since their experimental verification appears to be very difficult. Instead, measurements in electric fields are a more accessible experimental technique. The longitudinal electric field $`E_3`$ should be considered, since its influence on the physics of the phase transition the relevant characteristics of the KH2PO4 type crystals is analogous to the influence of the shear stress $`\sigma _6`$ and is well studied experimentally .

In this paper we shall show that the developed theory is capable, without introducing any additional fitting parameter, of describing the behavior of the phase transition, polarization, and other characteristics of a deuterated KD2PO4 in electric field $`E_3`$, and attempt to apply this theory also for the description of the relevant characteristics of a pure KH2PO4, with tunneling neglected.

## 2 Phenomenological analysis

Strictly speaking, for the KH2PO4 type crystals a expansion of thermodynamic potential $`G`$ in polarization $`P_3`$ and strain $`\epsilon _6`$

$`G=G_0+{\displaystyle \frac{1}{2}}\left(a_1P_3^2+a_2P_3\epsilon _6+a_3\epsilon _6^2\right)+{\displaystyle \frac{1}{4}}\left(b_1P_3^4+b_2P_3^3\epsilon _6+b_3P_3^2\epsilon _6^2\right)+`$ (2.1)
$`+{\displaystyle \frac{1}{6}}\left(c_1P_3^6+c_2P_3^5\epsilon _6+c_3P_3^4\epsilon _6^2\right)\overline{v}E_3P_3\overline{v}\sigma _6\epsilon _6`$
is the most consistent. It allows one to perform the analysis for the both fields conjugate to the order parameter – electric field $`E_3`$ and shear stress $`\sigma _6`$. Then the relevant order parameter, after which the phase transition takes place is a certain linear combination of $`P_3`$ and $`\epsilon _6`$. To determine it, a linear transformation $`(P_3,\epsilon _6)(\xi ,\zeta )`$ is performed, which diagonalizes the quadratic form $`(P_3,\epsilon _6)`$ in the expansion (2.1). Among $`\xi `$ and $`\zeta `$, the relevant order parameter is that one, which prefactor in (2.1) vanishes at the Curie point.

However, in practical calculations for the only experimentally accessible field conjugate to the order parameter – the electric field $`E_3`$, one usually uses the expansion in powers of polarization $`P_3`$

$$G=G_0+\frac{a^{}(TT_0)}{2}P^2+\frac{b}{4}P^4+\frac{c}{6}P^6EP,$$
(2.2)
and the higher order terms can be also taken into account. For the sake of simplicity, in this section we omit indices near polarization $`P_3`$ and field $`E_3`$.

In the vicinity of the transition temperature at $`E=0`$, the thermodynamic potential $`G(P)`$ has three minima $`P_{1,3}^2=(b\pm \sqrt{b^24ac})/2c`$ and $`P_2=0`$, the depths of which become equal at the transition point. Hence, the temperature of the first order phase transition $`T_{\mathrm{C0}}`$ at $`E=0`$ is found from the conditions

$$\frac{G}{P}=0,G(P_{1,3})=G(0),$$

that are equivalent to

$$3b^2=16ac,T_{\mathrm{C0}}=T_0+\frac{3b^2}{16ca^{}}.$$

The extremum points of the thermodynamic potential $`G(P)`$ at $`E0`$ are given by the equation

$$E=aP+bP^3+cP^5.$$
(2.3)
Among five solutions of this equations, two correspond to maxima, and three $`P_1<0`$, $`P_20`$, and $`P_3>0`$ correspond to minima of $`G(P)`$. From the condition

$$G(P_2)=G(P_3)\mathrm{at}E>0,G(P_1)=G(P_1)\mathrm{at}E<0,$$

in a linear in $`E`$ approximation we find a field dependence of the first order phase transition temperature (the phase equilibrium curve)

$$T_\mathrm{C}=T_{\mathrm{C0}}E\frac{12c}{7a^{}b}\sqrt{\frac{4c}{3b}}.$$

### 2.1 Critical point. Experimental measurements

The phase equilibrium curves (the first order phase transition lines) terminate in two critical points, which coordinates ($`\pm E^{},T^{}`$) follow from the thermodynamic conditions – equation of state and the equilibrium condition

$$\left(\frac{G}{P}\right)_E=0,\frac{E}{P}=0,\frac{^2E}{P^2}=0.$$

In these points a difference between the truly ferroelectric and pseudo -“paraelectric” with a non-zero polarization $`P_3`$ and strain $`\epsilon _6`$ phases disappears, so that the transition from one to the other takes place smoothly without jumps of the thermodynamic quantities.

Experimentally the coordinates of the critical points are usually found using the phenomenological theory, by measuring in some way the coefficients of the Landau expansion. To determine the critical field $`E^{}`$ and temperature $`T^{}`$, the following formulas are used ,

$`E^{}=a^{}P^{}+b(P^{})^3+c(P^{})^5+d(P^{})^7;`$
$`T^{}=T_0+{\displaystyle \frac{a^{}}{a^{}}}=T_0{\displaystyle \frac{3b(P^{})^2+5c(P^{})^4+7d(P^{})^6}{a^{}}},`$
where the higher order terms in the expansion are also taken into account, and $`P^{}`$ depends on the number of terms in the expansion

$`P^{}={\displaystyle \frac{5c}{2d}}\left[\sqrt{1{\displaystyle \frac{63}{25}}{\displaystyle \frac{bd}{c^2}}}1\right],c0,d0;`$
$`P^{}=\sqrt{{\displaystyle \frac{b}{7d}}},c=0,d0;`$
$`P^{}={\displaystyle \frac{3b}{10c}},c0,d=0.`$
The simplest is to find the coefficient $`a^{}`$, which is nothing but the inverse Curie constant of a crystal. The coefficients at higher terms in the expansion are determined by analyzing the field and temperature dependences of the crystal polarization. Usually, the analysis of the so-called $`\mathrm{\Gamma }`$-plots is performed. If one restricts the Landau expansion by the $`P^6`$ term, then from the equation for field (2.3) it follows , that the dependence of the quantity

$$\mathrm{\Gamma }(P^2)=\frac{EaP}{P^3}=b+cP^2$$

on $`P^2`$ must be linear and independent of the magnitude of the applied field. The intersection of this line with the ordinate axis $`(P^2)`$ gives a value of $`b`$, and its slope gives the coefficient $`c`$. Hence, by analyzing the experimentally measured dependence $`\mathrm{\Gamma }(P^2)`$ one is able to determine two coefficients of the Landau expansion.

When the dependence $`\mathrm{\Gamma }(P^2)`$ is closer to a quadratic one rather than to to linear one, we should neglect the term $`cP^5`$ in the Landau expansion and take into account the term $`dP^7`$, instead. Then the dependence

$$\mathrm{\Gamma }(P^4)=\frac{EaP}{P^3}=b+dP^4$$

must be linear.

Another, somewhat more sophisticated method of determination of the Landau coefficients was proposed by Schmidt . Instead of the $`\mathrm{\Gamma }`$-plots, the so-called isopols – lines of a constant polarization in the $`(E,T)`$ plane should be analyzed. From (2.3) it follows that

$$T=\frac{E}{a^{}P}+T_0\frac{bP^2+cP^4}{a^{}},$$

that is, the dependence $`T(E)`$ at constant polarization is linear. Approximating the experimental paraelectric isopols, one can find the coefficient $`a^{}`$ from the expression

$$a^{}=\frac{1}{P}\left(\frac{E}{T}\right)_P.$$

It should be noted that at the first order phase transition the isopols do intersect, whereas at the second order phase transition they do not. Therefore, this analysis permits one to determine the order of the phase transition and estimate the coordinates of the critical point (the point where the order of the phase transition changes), if one exists.

Unfortunately, the described method of determination of the critical point coordinates according to the Landau coefficients does not allow to find more or less trustworthy values of the critical quantities. In Table 1 we presented the measured in different papers Landau coefficients and calculated coordinates of the critical points for KH2PO4 (the Table is taken from ). All the present results agree as for the magnitude of the critical field in this crystal about 100-300 V/cm. We did not present here the data obtained within dilatometric X-rays studies , giving the critical field in KH2PO4 of about 8500V/cm.

As we see, a considerable discrepancy between values of the Landau coefficients takes place, and values of the critical point coordinates are very sensitive to the choice of the Landau coefficients. Thus, a 1.5 times increase of the $`b`$ coefficient leads to a 3 times as large value of the critical field and twice as large the quantity $`T^{}T_0`$. The main sources of differences in the values of critical coordinates determined via the Landau coefficients are the following

1. Inadequacy of the Landau expansion as such. It is known to be suitable for the second order phase transitions, only. For crystals, where the first order phase transition is observed, a large number of terms in the expansion should be taken into account, and even then it is valid only in the narrow vicinity of the transition point. Even for KH2PO4, where the jump of polarization at the transition point is not as large as in deuterated KD2PO4, the Landau expansion is not quite adequate.
2. Ambiguity of the Landau expansion. At interpretation of the same experimental data by different expansions  (with $`c=0`$, $`d0`$ or with $`c0`$, $`d=0`$) the critical field can change to more than 4 times. The expansion with $`c=0`$, $`d0`$ yields considerably smaller values of the critical field than the expansion with $`c0`$, $`d=0`$ does.
3. A large numerical error in calculations of the expansion coefficients at a given form of the expansion. Thus, at determining the coefficient $`b`$ from $`\mathrm{\Gamma }`$-plots, the error arises due to the data dispersion for $`\mathrm{\Gamma }(P^2)`$ at small values of polarization.
4. Changes in the Landau coefficients from sample to sample. First, a quite large dispersion of the data (as for determination of the critical point coordinates) takes place for the inverse Curie constant (the coefficient $`a^{}`$) . Similarly, the values of $`b`$ for different samples of the crystal do differ, even though they are obtained by the same method. Here, the dispersion of the data may exceed the error of measurement . Apparently, the Landau coefficients and, thereby, the coordinates of the critical point, essentially depend on a quality of the sample, its history, presence of inner defects, etc.
5. Different experimental methodics of polarization measurements (pyroelectric, dilatometric, hysteresis loops) give values of the coefficient $`b`$, which may significantly differ.

Comparison with experimental data of other quantities, calculated with the Landau expansion (for instance, temperature and field curves of polarization) does not allow to ascertain these coefficients, because these other quantities are not that sensitive to the values of the Landau coefficients, as the coordinates of the critical point.

Hence, due to a large error in determination of the Landau coefficients and ambiguity of the Landau expansion, the method of calculation of the critical fields and temperatures via the phenomenologic theory allows one only to estimate the coordinates of the critical point (order of magnitude of the critical field).

## 3 Microscopic model

We consider a ferroelectric crystal of the KH2PO4 type to which external electric field $`E_3`$, inducing polarization $`P_3`$ and strain $`\epsilon _6`$ in the high-temperature phase, is applied.

The entire Hamiltonian of the model  consists of a “seed” part, independent of a hydrogen subsystem configuration and attributed to a host lattice of heavy ions, and of pseudospin short-range and long-range hydrogen Hamiltonians, tunneling being neglected

$$H=N\overline{v}\left(\frac{c_{66}^{E0}}{2}\epsilon _6^2e_{36}^0E_3\epsilon _6\frac{\chi _{33}^0}{2}E_3^2\right)+H_{\mathrm{long}}+H_{\mathrm{short}}.$$
(3.4)
The “seed” energy expressed in terms of the electric field $`E_3`$ and strain $`\epsilon _6`$ includes the elastic, piezoelectric, and electric counterparts. $`c_{66}^{E0}`$, $`e_{36}^0`$, and $`\chi _{33}^0`$ are the so-called “seed” elastic constant, coefficient of the piezoelectric stress, and dielectric susceptibility, respectively; $`\overline{v}=v/k_\mathrm{B}`$, $`v`$ is the primitive cell volume; $`k_\mathrm{B}`$ is the Boltzmann constant; $`N`$ is the number of primitive cells.

$`H_{\mathrm{long}}`$ is the mean field Hamiltonian of the long-range dipole-dipole and lattice mediated  interactions between deuterons plus a linear in strain $`\epsilon _6`$ molecular field  induced by piezoelectric coupling

$`H_{\mathrm{long}}={\displaystyle \frac{1}{2}}{\displaystyle \underset{q^{}f^{}qf}{}}J_{ff^{}}(qq^{}){\displaystyle \frac{\sigma _{qf}}{2}}{\displaystyle \frac{\sigma _{q^{}f^{}}}{2}}{\displaystyle \underset{qf}{}}\left[\left({\displaystyle \underset{q^{}f^{}}{}}J_{ff^{}}(qq^{}){\displaystyle \frac{\sigma _{q^{}f^{}}}{2}}\right){\displaystyle \frac{\sigma _{qf}}{2}}2\psi _6\epsilon _6{\displaystyle \frac{\sigma _{qf}}{2}}\right]`$
$`=2N\nu \eta ^2{\displaystyle \underset{qf}{}}\left(2\nu \eta 2\psi _6\epsilon _6\right){\displaystyle \frac{\sigma _{qf}}{2}},`$ (3.5)
where

$$4\nu =J_{11}+2J_{12}+J_{13}$$

is the eigenvalue of the long-range interaction matrix Fourier transform $`J_{ff^{}}=_{𝐑_q𝐑_q^{}}J_{ff^{}}(qq^{})`$;

$$\eta =\sigma _{q1}=\sigma _{q2}=\sigma _{q3}=\sigma _{q4}$$

is the mean value of the Ising pseudospin $`\sigma _{qf}=\pm 1`$ which two eigenvalues are assigned to two equilibrium positions of a hydrogen on the $`f`$-th bond in the $`q`$-th unit cell.

The Hamiltonian of the short-range configurational interactions between hydrogens is usually chosen such as to reproduce the energy levels of the Slater-type model for KDP (see, for instance Ref. ) – the energy levels of up-down $`\epsilon _s`$ (twice degenerate at $`\epsilon _6=0`$ and $`E_3=0`$), lateral $`\epsilon _a`$ (four-fold degenerate), single-ionized $`\epsilon _1`$ (eight-fold degenerate), and double-ionized $`\epsilon _0`$ (twice degenerate) hydrogen configurations ($`\epsilon _s<\epsilon _a\epsilon _1\epsilon _0`$).

Since the system is no longer symmetric with respect to the reflection $`\sigma _h`$ in the $`ab`$ plane and mirror rotation $`S_4`$ around the $`c`$ axis (both operations change the sings of polarization and strain), in presence of strain $`\epsilon _6`$ and in the electric field $`E_3`$ a splitting of the energies of up and down ($`i=1`$ and $`i=2`$), lateral ($`i=5,6`$) and ($`i=7,8`$), and single ionized ($`i=9,10,11,12`$ and $`i=13,14,15,16`$) configurations takes place (confuguration numbers $`i`$ are given in Appendix). Since strain $`\epsilon _6`$ and polarization $`P_3`$ transform after the same irreducible representation ($`B_2`$ in the paraelectric phase and $`A_1`$ in the ferroelectric phase), the field $`E_3`$ does not split those levels which remain degenerate in presence of the strain $`\epsilon _6`$.

That part of the splitting, which origin is the distortion of the PO4 groups and changes of the angle between perpendicular in the paraelectric phase hydrogen bonds is described by linear functions of the strain $`\epsilon _6`$. The contribution of the electric field $`E_3`$ to the splitting is taken to be equal to the difference between the energy levels of the groups dipoles in the longitudinal field $`E_3`$. Since the groups K-DnPO4 with hydrogens in up ($`i=1`$) and down ($`i=2`$) configurations and in single-ionized configurations (configurations $`i=9,10,11,12`$ and $`i=13,14,15,16`$) have oppositely directed projections of the dipole moments $`𝝁_i`$ on the axis $`c`$, these groups have also different energies $`𝝁_i𝐄`$ in external electric field . Usually, the absolute values of the $`c`$-projections of the dipole moments of up/down configurations $`\mu _3`$ are assumed to be twice as large as the corresponding projections of single-ionized configurations. The $`c`$-projections of dipole moments of lateral and double-ionized groups are zero.

Finally, the Hamiltonian of the short-range interactions rewritten in terms of pseudospins according to standard rules  and taken into account within the most appropriate for these crystals four-particle cluster approximation, is

$`\widehat{H}_{\mathrm{short}}=[\mathrm{\Delta }+\mu _3E_3{\displaystyle \frac{2\delta _{16}\delta _{s6}}{4}}\epsilon _6]{\displaystyle \underset{q}{}}{\displaystyle \underset{f=1}{\overset{4}{}}}{\displaystyle \frac{\sigma _{qf}}{2}}+{\displaystyle \underset{q}{}}\{U[{\displaystyle \frac{\sigma _{q1}}{2}}{\displaystyle \frac{\sigma _{q3}}{2}}+{\displaystyle \frac{\sigma _{q2}}{2}}{\displaystyle \frac{\sigma _{q4}}{2}}]+\mathrm{\Phi }{\displaystyle \frac{\sigma _{q1}}{2}}{\displaystyle \frac{\sigma _{q2}}{2}}{\displaystyle \frac{\sigma _{q3}}{2}}{\displaystyle \frac{\sigma _{q4}}{2}}+`$
$`\epsilon _6(\delta _{s6}+2\delta _{16})[{\displaystyle \frac{\sigma _{q1}}{2}}{\displaystyle \frac{\sigma _{q2}}{2}}{\displaystyle \frac{\sigma _{q3}}{2}}+{\displaystyle \frac{\sigma _{q1}}{2}}{\displaystyle \frac{\sigma _{q2}}{2}}{\displaystyle \frac{\sigma _{q4}}{2}}+{\displaystyle \frac{\sigma _{q1}}{2}}{\displaystyle \frac{\sigma _{q3}}{2}}{\displaystyle \frac{\sigma _{q4}}{2}}+{\displaystyle \frac{\sigma _{q2}}{2}}{\displaystyle \frac{\sigma _{q3}}{2}}{\displaystyle \frac{\sigma _{q4}}{2}}]`$ (3.6)
$`+(V+\delta _{a6}\epsilon _6)[{\displaystyle \frac{\sigma _{q1}}{2}}{\displaystyle \frac{\sigma _{q2}}{2}}+{\displaystyle \frac{\sigma _{q3}}{2}}{\displaystyle \frac{\sigma _{q4}}{2}}]+(V\delta _{a6}\epsilon _6)[{\displaystyle \frac{\sigma _{q2}}{2}}{\displaystyle \frac{\sigma _{q3}}{2}}+{\displaystyle \frac{\sigma _{q4}}{2}}{\displaystyle \frac{\sigma _{q1}}{2}}]\}.`$
Detailed derivation of the Hamiltonian and the table of the split energy levels in presence of external electric field (longitudinal and transverse) are given in Appendix.

In Eq. (3.6) the following notations are used

$$V=\frac{1}{2}w_1,U=\frac{1}{2}w_1\epsilon ,\mathrm{\Phi }=4\epsilon +2w_18w;$$

where

$$\epsilon =\epsilon _a\epsilon _s,w=\epsilon _1\epsilon _s,w_1=\epsilon _0\epsilon _s$$

are the so-called Slater energies. Splitting of the energy levels due to lowering the system symmetry is the only changes in the short-range interactions that we take into account within this model. Therefore, $`\epsilon `$, $`w`$, $`w_1`$ do not depend on strain $`\epsilon _6`$ of field $`E_3`$.

The condition of equality of the mean values of pseudospins $`\eta =\sigma _{qf}`$ calculated with the four-particle (3.6) and single-particle deuteron Hamiltonians (see ) permits to exclude the self-consistency parameter $`\mathrm{\Delta }`$. The order parameter $`\eta `$ and strain $`\epsilon _6`$ can be found by minimization of the thermodynamic potential (Gibbs’ function) $`g_{1E}(T,\sigma _6,E_3,\eta )`$

$`g_{1E}(T,\sigma _6,E_3,\eta )={\displaystyle \frac{\overline{v}}{2}}c_{66}^{E0}\epsilon _6^2\overline{v}e_{36}^0\epsilon _6E_3{\displaystyle \frac{\overline{v}}{2}}\chi _{33}^{\epsilon 0}E_3^2+2T\mathrm{ln}2+2\nu \eta ^22T\mathrm{ln}(1\eta ^2)D\overline{v}\sigma _6\epsilon _6,`$
where

$`D=\mathrm{cosh}(2z+\beta \delta _{s6}\epsilon _6)+4b\mathrm{cosh}(z\beta \delta _{16}\epsilon _6)+aa_6+{\displaystyle \frac{a}{a_6}}+d,`$
$`z={\displaystyle \frac{1}{2}}\mathrm{ln}{\displaystyle \frac{1+\eta }{1\eta }}+\beta \nu \eta \beta \psi _6\epsilon _6+{\displaystyle \frac{\beta \mu _3E_3}{2}},`$
$`a=\mathrm{exp}(\beta \epsilon ),b=\mathrm{exp}(\beta w),d=\mathrm{exp}(\beta w_1),a_6=\mathrm{exp}(\beta \delta _{a6}\epsilon _6).`$
The conjugate to the strain $`\epsilon _6`$ stress $`\sigma _6`$ is introduced for the sake of simplicity; in numerical calculations $`\sigma _6=0`$.

Using the system of equations

$`\sigma _6=c_{66}^{E0}\epsilon _6e_{36}^0E_3+{\displaystyle \frac{4\psi _6}{\overline{v}}}{\displaystyle \frac{m}{D}}+{\displaystyle \frac{2M_6}{\overline{v}D}},`$
$`P_3=e_{36}^0\epsilon _6+\chi _{33}^{\epsilon 0}E_3+2{\displaystyle \frac{\mu _3}{v}}{\displaystyle \frac{m}{D}},`$
which follows from the thermodynamic equilibrium conditions

$$\frac{1}{\overline{v}}\left(\frac{g_{1E}}{\epsilon _6}\right)_{T,E_3,\sigma _6}=0,\frac{1}{\overline{v}}\left(\frac{g_{1E}}{E_3}\right)_{T,\sigma _6}=P_3$$

we find the isothermal dielectric susceptibility of a free crystal (at $`\sigma _6=`$const)

$$\chi _{33}^{T\sigma }=\left(\frac{P_3}{E_3}\right)_{T\sigma _6}=\chi _{33}^{T\epsilon }+\frac{(e_{36}^T)^2}{c_{66}^{TE}},$$
(3.7)
expressed via the isothermal dielectric susceptibility of a clamped crystal (at $`\epsilon _6=`$const)

$$\chi _{33}^{T\epsilon }=\left(\frac{P_3}{E_3}\right)_{T\epsilon _6}=\chi _{33}^0+\frac{\mu _3^2}{v}\frac{2\beta \varkappa }{D2\varkappa \phi },$$
(3.8)
the isothermal coefficient of piezoelectric stress

$$e_{36}^T=\left(\frac{P_3}{\epsilon _6}\right)_{T,E_3}=e_{36}^0+\frac{2\mu _3}{v}\frac{\beta \theta }{D2\varkappa \phi },$$
(3.9)
and the isothermal elastic constant at constant field

$`c_{66}^{TE}=\left({\displaystyle \frac{\sigma _6}{\epsilon _6}}\right)_{T,E_3}=c_{66}^{E0}+{\displaystyle \frac{8\beta \psi _6}{\overline{v}}}{\displaystyle \frac{\varkappa \psi _6+r}{D2\varkappa \phi }}+{\displaystyle \frac{2\beta }{\overline{v}D^2}}M_6^2`$
$`{\displaystyle \frac{2\beta }{\overline{v}D}}\left[\delta _{s6}^2\mathrm{cosh}(2z+\beta \delta _{s6}\epsilon _6)+\delta _{a6}^2(aa_6+{\displaystyle \frac{a}{a_6}})+4b\delta _{16}^2\mathrm{cosh}(z\beta \delta _{16}\epsilon _6)\right]{\displaystyle \frac{4\phi r^2}{\overline{v}TD(D2\varkappa \phi )}}.`$
The other isothermal dielectric and piezoelectric characteristics can be recalculated via the found above by using the known formulas

the constant of piezoelectric stress $`h_{36}`$

$$h_{36}=\left(\frac{E_3}{\epsilon _6}\right)_{TP_3}=\left(\frac{\sigma _6}{P_3}\right)_{T\epsilon _6}=\frac{e_{36}^T}{\chi _{33}^{T\epsilon }}$$
(3.10)
the elastic constant $`c_{66}^P`$ at constant polarization

$$c_{66}^P=\left(\frac{\sigma _6}{\epsilon _6}\right)_{TP_3}=c_{66}^{TE}+e_{36}^Th_{36}.$$
(3.11)
compliance at constant field

$$s_{66}^{TE}=\left(\frac{\epsilon _6}{\sigma _6}\right)_{TE_3}=\frac{1}{c_{66}^{TE}},$$
(3.12)
the coefficient of the piezoelectric strain

$$d_{36}^T=\left(\frac{P_3}{\sigma _6}\right)_{TE_3}=e_{36}^Ts_{66}^{TE},$$
(3.13)
the constant of piezoelectric strain

$$g_{36}=\left(\frac{E_3}{\sigma _6}\right)_{TP_3}=\frac{h_{36}}{c_{66}^{TP}},$$
(3.14)
When dynamic experimental methodics are used (measuring frequency exceeds the thermal relaxation frequency), not the isothermal but adiabatic characteristics of the crystals are measured. In the paraelectric phase in absence of electric field the adiabatic and isothermal quantities coincide, but they may essentially differ in the ferroelectric phase or in the electric field. The adiabatic quantities can be obtained from the isothermal analogs with the help of the following formulas

$`{\displaystyle \frac{1}{\chi _{33}^{S\sigma }}}={\displaystyle \frac{1}{\chi _{33}^{T\sigma }}}\left[1+{\displaystyle \frac{1}{\chi _{33}^{T\sigma }}}{\displaystyle \frac{(P_3/T)_{E_3}^2}{(S/T)_{P_3}}}\right]={\displaystyle \frac{1}{\chi _{33}^{T\sigma }}}\left[1+{\displaystyle \frac{T}{\chi _{33}^{T\sigma }}}{\displaystyle \frac{p_\sigma ^2}{c_{P_3,\sigma }}}\right];`$
$`d_{36}^S=d_{36}^T{\displaystyle \frac{\chi _{33}^{S\sigma }}{\chi _{33}^{T\sigma }}};`$ (3.15)
$`(c_{66}^{SE})^1=(c_{66}^{TE})^1\left(1{\displaystyle \frac{\chi _{33}^{S\sigma }}{\chi _{33}^{T\sigma }}}\right){\displaystyle \frac{(d_{36}^T)^2}{\chi _{33}^{T\sigma }}},`$
where

$$S=R\left(2\mathrm{ln}2+2\mathrm{ln}[1\eta ^2]+2\mathrm{ln}D+4T\phi ^T\eta +\frac{2\overline{M}_6}{D}\right)$$

is the entropy of the hydrogen subsystem, $`p_\sigma `$ is the pyroelectric coefficient, $`c_{P_3,\sigma }`$ is the specific heat at constant polarization and pressure. From (3) it follows that the most prominent difference between the adiabatic and isothermal quantities takes place in the range of rapid temperature changes of polarization (where $`(P_3/T)_{E_3}^2`$ is large) – in the vicinity of the transition point or of the permittivity maximum.

Using (3) and the relations (3.7)-(3.14) we can show that the adiabatic and isothermal “true” constants of the crystals – the elastic constant at constant polarization $`c_{66}^P`$ and piezomodules $`h_{36}`$ and $`g_{36}`$ – coincide.

The pyroelectric coefficient and the contribution of the hydrogen subsystem into the specific heat at constant pressure and polarization are given by the following expressions

$$p_6^\sigma =p_6^\epsilon +e_{36}\alpha _6,$$
(3.16)
and

$$\mathrm{\Delta }c_{P_3,\sigma }=\frac{T}{v}\left(\frac{S}{T}\right)_\sigma =\mathrm{\Delta }c_{P_3\epsilon }+\frac{q_6^P\alpha _6}{v},$$
(3.17)
where $`\mathrm{\Delta }c_{P_3\epsilon }`$ is the specific heat at constant polarization and strain

$$\mathrm{\Delta }c_{P_3,\epsilon }=\frac{T}{v}\left(\frac{S}{T}\right)_{P_3,\epsilon _6}=\frac{2R}{D}\left\{4T\phi ^T[\varkappa T\phi ^T+\stackrel{~}{q}_6]+N_6\frac{\overline{M}_{6}^{}{}_{}{}^{2}}{D}\right\},$$

$`R`$ is the gas constant; $`q_6^P`$ is the strain heat at constant $`P_3`$,

$$q_6^P=\left(\frac{S_6}{\epsilon _6}\right)_{P_3,T}=\frac{4R}{D}\left\{T\phi _6^T(r2\varkappa _6\psi _6)\stackrel{~}{q}_6\psi _6\lambda _6+\frac{\overline{M}_6M_6}{2D}\right\},$$

$`\alpha _6`$ is the factor produced by temperature variation of the strain $`\epsilon _6`$

$$\alpha _6=\left(\frac{\epsilon _6}{T}\right)_\sigma =\frac{q_6^P+h_{36}p_6^\epsilon }{c_{66}^E}$$

(true thermal expansion, which invokes the diagonal strains, is not considered here. We used the following notations

$`N_6={\displaystyle \frac{1}{T^2}}[(\epsilon +\delta _{a6}\epsilon _6)^2aa_6+(\epsilon \delta _{a6}\epsilon _6)^2{\displaystyle \frac{a}{a_6}}+4bw\delta _{16}\epsilon _6\mathrm{sinh}(z\beta \delta _{16}\epsilon _6)+`$
$`+4b[w^2+\delta _{16}^2\epsilon _6^2]\mathrm{cosh}(z\beta \delta _{16}\epsilon _6)+w_{1}^{}{}_{}{}^{2}d\left(\delta _{s6}\epsilon _6\right)^2\mathrm{cosh}(2z+\beta \delta _{a6}\epsilon _6)];`$
$`\stackrel{~}{q}_6={\displaystyle \frac{1}{T}}\left[\delta _{s6}\epsilon _6\mathrm{cosh}(2z+\beta \delta _{as}\epsilon _6)+2b\delta _{16}\epsilon _6\mathrm{cosh}(z\beta \delta _{16}\epsilon _6)+2bw\mathrm{sinh}(z\beta \delta _{16}\epsilon _6)\right]\eta \overline{M}_6,`$
$`\lambda _6={\displaystyle \frac{1}{T}}[\delta _{s6}^2\epsilon _6\mathrm{sinh}(2z+\beta \delta _{a6}\epsilon _6)+\delta _{16}^2\epsilon _64b\mathrm{cosh}(z_6\beta \delta _{16}\epsilon _6)+`$
$`+\delta _{a6}(aa_6(\epsilon +\delta _{a6}\epsilon _6){\displaystyle \frac{a}{a_6}}(\epsilon \delta _{a6}\epsilon _6))+\delta _{16}w\epsilon _64b\mathrm{sinh}(z\beta \delta _{16}\epsilon _6)].`$
$`\phi ^T=\beta ^2(\nu \eta \psi _6\epsilon _6),`$
$`\overline{M}_6=\beta (4bw\mathrm{cosh}z+dw_1+a\epsilon a_6+a\epsilon a_6^1+M_6\epsilon _6).`$
$`R`$ is the gas constant.

Having the pyroelectric coefficient and the specific heat at constant polarization, we can find the total molar specific heat at constant pressure

$$\mathrm{\Delta }c_6^\sigma =T\left(\frac{S}{T}\right)_\sigma =\mathrm{\Delta }c_6^{P\sigma }+q_6^\epsilon p_6^\sigma .$$
(3.18)
$$q_6^\epsilon =\left(\frac{S}{P_3}\right)_{\epsilon _6,T}=\frac{v}{\mu _3}\frac{2RT}{D}\phi \{2\varkappa T\phi ^T+\stackrel{~}{q}_6\}$$

is the polarization heat at given $`\epsilon _6`$,

## 4 Discussion

### 4.1 Fitting procedure

The presented in previous Section theoretical results will be used to description of the physical characteristics of a highly deuterated crystal KD2PO4. We shall also verify whether the presented theory is capable of describing behavior of the physical characteristics of an undeuterated KH2PO4 without taking into account tunneling effects.

For a highly deuterated crystal K(H1-xD$`{}_{x}{}^{})_2`$PO4 with the transition temperature in zero field $`T_{\mathrm{C0}}=211.73`$ K (a nominal deuteration level $`x=0.89`$, hereafter abbreviated as KD2PO4) we use the values of the theory parameters found in , providing a fair quantitative description of temperature of several associated with strain $`\epsilon _6`$ dielectric, piezoelectric, and elastic characteristics of the crystal at atmospheric pressure, namely, the dielectric permittivities of a free and clamped crystals, elastic constants $`c_{66}^E`$ and $`c_{66}^P`$ of open-circuited and short-circuited crystals, and piezomodules $`e_{36}`$, $`d_{36}`$, $`g_{36}`$ and $`h_{36}`$. Details of the fitting procedure are given in .

For and undeuterated crystal KH2PO4 we also chose the theory parameters such as to fit the temperature behavior of the elastic constants $`c_{66}^E`$ and $`c_{66}^P`$, piezomodules $`e_{36}`$, $`d_{36}`$, $`g_{36}`$, and $`h_{36}`$, as well as the longitudinal static dielectric permittivity of a clamped crystal $`\epsilon _{33}^\epsilon `$. It should be noted that only the data of  for the temperature dependences of the coefficient of piezoelectric strain $`d_{36}`$, of  for the dielectric permittivity $`\epsilon _{33}^\sigma `$, and of  for the elastic constant $`s_{66}^E`$ are direct experimental points for KH2PO4. Using Eqns. (3.7) – (3.14) and having the values of $`d_{36}`$, $`\epsilon _{33}^\sigma `$, and $`c_{66}^E`$, we find “experimental” points for the piezoelectric constants $`e_{36}`$, $`h_{36}`$, $`g_{36}`$, elastic characteristics $`c_{66}^P`$, $`s_{66}^E`$, $`s_{66}^P`$, and clamped dielectric permittivity $`\chi _{33}^\epsilon `$. Recalculated thus values of the piezoelectric constants $`g_{36}5310^8`$ cm2/esu and $`h_{36}3.810^4`$ dyn/esu above the transition point are greater than $`4410^8`$ cm2/esu and $`3.010^4`$ dyn/esu, respectively, given by Mason  but closer to the deQuervain values ($`5010^8`$ cm2/esu for $`h_{36}`$).

By this set of the parameters we also try to describe the field dependences of polarization $`P_3`$ , longitudinal static dielectric susceptibility $`\chi _{33}^{S\sigma }`$ and elastic constant $`c_{66}^{SE}`$ of a KH2PO4, obtained in . It should be noted that in  only the elastic constant was measured directly by the ultrasonic technique, whereas the susceptibility was recalculated using the known thermodynamic relations and the data of  for the piezomodules.

A scheme of choosing the theory parameters for KH2PO4 was analogous to that for KD2PO4. At chosen $`\epsilon `$ and $`w`$, close to those used in theories where the piezoelectricity and tunneling effects are not taken into account , and setting the Curie temperature of a clamped crystal $`T_0^{\mathrm{clamp}}=118.65`$ K, we found the value of the long-range interaction parameter $`\nu `$. Setting the values of the deformation potentials $`\psi _6`$, $`\delta _{a6}`$, $`\delta _{16}`$, we found the value $`\delta _{s6}`$ by fitting to experimental value of the piezomodule $`e_{36}`$ at a certain temperature. The parameters $`\epsilon `$, $`w`$, $`\psi _6`$, $`\delta _{a6}`$, $`\delta _{16}`$, $`c_{66}^{E0}`$, $`\mu _3/v`$ were chosen such as to obtain the correct values of the transition temperature $`T_{\mathrm{C0}}=122.8`$ K  of a free crystal, ratio of the polarization jump at the transition point to saturation polarization (jump of the order parameter), correct temperature curves of the elastic constants $`c_{66}^E`$  and $`c_{66}^P`$, piezomodules $`d_{36}`$, $`g_{36}`$, and $`h_{36}`$, longitudinal static dielectric permittivities of a free $`\epsilon _{33}^\sigma `$  and clamped $`\epsilon _{33}^\epsilon `$ crystals, as well as specific heat. Properly chosen parameters $`e_{36}^0`$, $`\chi _{33}^{(0)}`$ yield the correct values of the piezomodules $`d_{36}`$, $`e_{36}`$, $`g_{36}`$, and $`h_{36}`$ in the high-temperature limit.

In Table 2 we present the adopted values of the theory parameters for KD2PO4 and KH2PO4.

### 4.2 Effective dipole moment

In our calculations, as well as in earlier theories (see, for instance, ) two different values of the effective dipole moment $`\mu _3^{}<\mu _3^+`$ must be used in the ferroelectric and paraelectric phases. The value of $`2\mu _3^{}/v`$ in the ferroelectric phase is given by the experimental value of saturation polarization. The paraelectric values of $`2\mu _3^+/v`$, listed in Table 2, are set by the relation between the experimental and theoretical values of the Curie constant for the longitudinal static dielectric permittivity. In the present theory, $`\mu _3^+`$ must also provide an agreement with experiment for the piezomodules

$$e_{36}\mu _3,d_{36}\mu _3,h_{36}\mu _{3}^{}{}_{}{}^{1},g_{36}\mu _{3}^{}{}_{}{}^{1}$$

in the paraelectric phase. In KH2PO4 and KD2PO4 the ratio $`\mu ^+/\mu ^{}`$ is about 1.2. Neither in the present model nor in simpler versions of the proton ordering models it is possible to choose the theory parameters such as to fit the temperature curves of polarization and permittivity with a single value of the parameter $`\mu _3`$.

The necessity to use in calculations two different values of $`\mu `$ for paraelectric and ferroelectric phases is not a problem while we do not consider behavior of the system in external fields conjugate to the order parameter. These fields smear out the phase transition; therefore, when the difference between the phases becomes only quantitative (in fields above the critical one), it does not make sense to distinguish the paraelectric and ferroelectric phase and the corresponding $`\mu ^+`$ and $`\mu ^{}`$.

Tokunaga  relates the deviation of the ratio $`\mu ^+/\mu ^{}`$ from unity with the existence of an underdamped soft mode in a crystal. In the displacive type ferroelectrics $`\mu ^+/\mu ^{}1`$, whereas in the order-disorder type ferroelectrics $`\mu ^+/\mu ^{}1`$. Failure of the order-disorder model to describe both polarization and dielectric permittivity without invoking two values of $`\mu `$ for different phases shows the limits of the model suitability. Since the KH2PO4 family crystals undergo phase transitions of a mixed ordering-displacive type (it is believed that hydrogen ordering triggers displacements of heavy ions), for a consistent description of dielectric properties of these crystals, we need to sophisticate the model and include phonon degrees of freedom and anharmonicity into consideration. Moreover, we need to go further than Kobayashi model (mixed proton-phonon model with only one optical mode taken into account), which is known only to renormalize parameters of the proton ordering model.

### 4.3 Zero field case

Figures 1 and 2 illustrate how the proposed theory describes experimental data for the physical characteristics of KD2PO4 and KH2PO4 crystals in absence of external electric field. Polarization of a pure KH2PO4 $`P_3`$ is calculated with $`2\mu _3^{}/v=5.0\mu `$C/cm. To obtain the total specific heat, we added a constant term 60 J/mol K, describing the background specific heat of a host lattice of heavy ions, to the calculated from (3.18) contribution of the hydrogen subsystem to the specific heat.

### 4.4 Non-zero field case

In figure 3 we plot the $`T_\mathrm{C}E_3`$ phase diagrams of the KD2PO4 and KH2PO4 crystals. These diagrams are of the same topology as the $`T_\mathrm{C}\sigma _6`$ diagram of KD2PO4 . The coordinates of the critical point, calculated within the microscopic theory, essentially depend on the magnitude of the order parameter jump $`\mathrm{\Delta }\eta `$ (the ratio of the polarization jump to the saturation polarization) at the transition point in zero field. Since the order of the phase transition in a pure KH2PO4 is close to the second one, while in a deuterated KD2PO4 a pronounced jump of polarization at the transition point takes place, the critical field in KH2PO4 is much lower than that in KD2PO4.

For KD2PO4 we obtain a good agreement with experimental data for a field dependence of the transition temperature : $`T_\mathrm{C}/E_3=0.13`$K/ kVcm in our model and $`0.125\pm 0.1`$ in . Theoretical value of the critical field $`E_3^{}=7.0`$ kV/cm, where the phase transition in the system disappears, accords fairly well with the experimental estimate $`7.1\pm 0.6`$ kV/cm . The critical temperature $`T^{}=212.6`$ K is close to that from the $`T_\mathrm{C}\sigma _6`$ diagram.

For an undeuterated crystal, the theory gives the following characteristics of the phase diagram

| $`E^{}=105`$ V/cm, | $`T^{}T_0=0.05`$ K, | $`T_\mathrm{C}/E_3=0.23`$K/ kVcm. |
| --- | --- | --- |

The calculated critical field in KH2PO4 agrees with the the estimates $`80÷370`$ V/cm , obtained via experimentally measured coefficients of Landau expansions. However, at varying the microscopic $`\mathrm{\Delta }\eta `$ within experimentally estimated limits (for which slight changes in the theory parameters are required), the calculated critical field is significantly increased, while more or less precisely measured macroscopic characteristics (e.g. permittivity) remain practically unchanged. We may conclude that the microscopic theory is able only to estimate the coordinates of the critical point.

In addition, in fields close to critical, peaks of the longitudinal permittivity or other characteristics having peculiarities at the transition point are very sharp. Therefore, even small changes of temperature ($`10^3`$ K) can change the permittivity value several times. The maximal temperature step in calculations, yielding more or less correct value of the permittivity maximum, is $`10^4`$ K.

As we have already mentioned, we cannot describe polarization of the crystals, without introducing the “ferroelectric” values of the dipole moment $`\mu _3`$. Nevertheless, we can compare the field behavior of the order parameter $`\eta `$ with the experimental data for the ratio $`P_3/P_s`$. Here $`P_s=5.0\mu `$C/cm2 for KH2PO4 and $`6.2\mu `$C/cm2 for KD2PO4 are the experimental values of saturation polarization, practically independent of external field . Such comparison is justified, since the contributions to polarization from the terms $`\chi _{33}^0E_3`$ and $`e_{36}^0\epsilon _6`$ are not essential. Figure 4 shows a fair accordance of theoretical temperature and field dependences of $`P_3/P_s`$ for KH2PO4 and KD2PO4 with the experimental data. Increase of polarization and vanishing of polarization jump are well reproduced by the theory.

In figure 5 we depicted the temperature dependences of two characteristics – isothermal static dielectric permittivity of a free crystal $`\epsilon _{33}^{T\sigma }`$ and the piezomodule $`h_{36}`$ of a deuterated crystal at different values of external electric field. Temperature curves of other characteristics of the crystal exhibiting peculiarities at the transition point – compliance $`s_{66}^E`$ and piezomodules $`d_{36}`$ and $`e_{36}`$ – are similar to those of the permittivity $`\epsilon _{33}^{T\sigma }`$. Temperature and field behavior of the piezomodule $`g_{36}`$ to those of $`h_{36}`$. The corresponding curves for a undeuterated are qualitatively similar, however, due to closeness of the order of the phase transition to the second one, the temperature and field intervals where all these changes take place are much more narrow.

Maximal values of $`\epsilon _{33}^{T\sigma }`$ and similar quantities shift to higher temperatures with field. As the field approaches its critical value, the peak values of these quantities in the transition points increase and are maximal at the critical point. The higher fields smear out the phase transition and round off and lower down the peaks.

The field effects on piezomodules $`h_{36}`$ and $`g_{36}`$ is similar to its effects on polarization. On increasing the field, jumps of these quantities at the transition point decrease and vanish at the critical field. At higher fields, these quantities exhibit smooth temperature dependences.

It is interesting to note that field dependences of adiabatic quantities are stronger that those of the isothermal quantities. Thus, as fig. 6 where we present temperature curves of the adiabatic and isothermal piezomodule $`d_{36}^S`$ of a pure KH2PO4 shows, the peak values of the adiabatic piezomodule (as well as of $`s_{66}^{SE}`$, $`e_{36}^S`$, $`\epsilon _{33}^S`$) decrease with the external field (above the critical point) much stronger than the peak values of the isothermal $`d_{36}^T`$, and the maxima of the adiabatic quantities shift with the field much more perceptibly that those of the isothermal quantities.

As one can see (Fig. 7), the proposed theory yields a fair agreement with experiment for the field effects on the adiabatic longitudinal dielectric susceptibility of a free crystal and elastic constant $`c_{66}^{SE}`$ in a pure KH2PO4 . Deviation of the theoretical curves from experimental points in the vicinity of the “transition” (maximum of the permittivity) is attributed to our neglecting tunneling effects. Such neglecting worsens an agreement with an experiment for the temperature curve of order parameter $`P_3/P_s`$ and, thereby, of $`\chi _{33}^{S\sigma }`$ and $`c_{66}^{SE}`$.

## 5 Concluding remarks

In this paper we apply the previously developed microscopic theory to description of effects produced by the longitudinal electric field $`E_3`$ on the phase transition and physical properties of the KH2PO4 family ferroelectrics. Calculations are performed in the four-particle cluster approximation within the proton ordering model without taking into account the tunneling effects. The developed model takes into account the existence of the shear strain $`\epsilon _6`$, which is spontaneous in the ordered phase and induced by the stress $`\sigma _6`$ and electric field $`E_3`$ (via the piezoeffect) in the disordered phase. We also take into account other effects induced by this strain – the splitting of short-range proton correlation energies and appearance of effective molecular fields, created by piezoelectric coupling.

The presented model provides a fair agreement with experimental data for temperature behavior (at zero field) of the dielectric, piezoelectric, elastic, and thermal characteristics – second derivatives of thermodynamic potentials (dielectric permittivity, piezomodules, elastic constants, specific heat) of the crystals. Such agreement takes place for a deuterated crystal KD2PO4 and for a pure KH2PO4 without taking into account the tunneling.

The model satisfactorily reproduced the parameters of experimental $`T_\mathrm{C}E_3`$ phase diagrams of KD2PO4 and KH2PO4. The transition temperature increases with field; this is accompanied by increase in polarization in the high-temperature phase and decrease of its jump at the transition point. The phase equilibrium curves terminate in the critical points, where the polarization (order parameter) jump vanishes. At higher fields the temperature curves of polarization and strain $`\epsilon _6`$ are smooth. Such behavior is typical for the systems undergoing the first order phase transitions in external fields conjugate to the order parameter.

The magnitude of the critical field essentially depends on the degree of the “first-orderness” of the phase transition). Thus, in KH2PO4 where the phase transition is close to the tricritical point, the critical field is several times smaller than in KD2PO4, where a pronounced first order phase transition takes place. Experimental method of the critical coordinates determination based in the phenomenologic analysis allows only to estimate the critical field. The calculated within the microscopic theory value of the critical field is determined by the magnitude of the order parameter at the transition point. Since on changing this quantity (at the proper and slight change of the relations between the theory parameters) within the limits of experimental estimates the calculated critical field significantly increases, the microscopic approach also permits only to estimate the coordinates of the critical point, though this estimate is better than the phenomenologic one.

As the field approaches the critical point, the peak values of thermodynamic quantities that have peculiarities at the transition point (the longitudinal dielectric permittivity $`\epsilon _{33}`$, piezomodules $`d_{36}`$ and $`e_{36}`$, and the elastic compliance $`s_{66}^E`$) increase, while the jumps of “true” constants of the crystals (piezomodules $`g_{36}`$ and $`h_{36}`$, and elastic constant $`c_{66}^P`$) decrease. At the critical point the peak values of the formers are maximal, whereas the jumps of the latters vanish. In fields above the critical one, temperature dependences of all thermodynamic quantities are smooth, and the maximal values of the characteristics that have peculiarities at the transition point decrease.

In presence of external field, there arise a difference between isothermal and adiabatic characteristics (dynamic methods of measurements yield the adiabatic quantities), which have peculiarities at the transition point. The field dependences of the adiabatic quantities are stronger than those of the isothermal quantities. Thus, in fields above the critical one, the peak values of the adiabatic quantities decrease with the field much faster that the peaks of the isothermal quantities, and the maxima of the adiabatic quantities shift to higher temperatures that the maxima of the isothermal quantities at the same field. Within the proposed theory we obtain a fair description of the experimental data for the field dependences of the adiabatic dielectric susceptibility and elastic constant of KH2PO4.

The developed model, as well all earlier used versions of proton ordering model, requires two different values of effective dipole moment to be introduced for description of polarization and dielectric permittivity of the crystals (in paraelectric and ferroelectric phases). For a consistent description of dielectric properties of these crystals, phonon degrees of freedom and anharmonicity must be taken into account.

## Acknowledgments

Authors would like to thank participants of the I Ukrainian-French Meeting on Ferroelectricity (Kiev, Ukraine, May 2000) for their interest to our results. This work was supported by the Foundation for Fundamental Investigations of the Ukrainian Ministry in Affairs of Science and Technology, project No 2.04/171.


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# 1 Introduction

## 1 Introduction

Let $`𝐠`$ be a finite-dimensional simple Lie algebra over $``$ and $`U_q(𝐠)`$ be the corresponding quantized enveloping algebra over $`[v,v^1]`$. Let

$$U_q(𝐠)=U_q^{}U_q^0U_q^+$$

be the triangular decomposition of $`U_q(𝐠)`$. Let $`𝐁`$ be the canonical basis of $`U_q^{}`$, introduced independently by Lusztig and Kashiwara. It is natural to ask how the elements of $`𝐁`$ are expressed in terms of the generators $`F_1,F_2,\mathrm{},F_n`$ of $`U_q^{}`$. This is a difficult question which is known completely in only a few low rank cases, but the attempt to understand it has led to a remarkable theory of piecewise-linear combinatorics associated with the canonical basis.

In this paper we consider only the case in which $`𝐠`$ has type $`A_n`$. We describe the situation for small values of $`n`$ before giving some speculations for arbitrary $`n`$.

First suppose that $`𝐠`$ has type $`A_1`$. We write:

$``$ $`=`$ $`\{a:a0\},`$
$`\left[a\right]`$ $`=`$ $`{\displaystyle \frac{v^av^a}{vv^1}},\text{for }a,`$
$`\left[a\right]!`$ $`=`$ $`[1][2]\mathrm{}[a],\text{for }a,`$
and $`F_1^{(a)}=F_1^a/[a]!`$.

It was shown by Lusztig  that $`𝐁=\{F_1^{(a)}:a\}`$. Thus the canonical basis elements are the quantized divided powers of the generator $`F_1`$.

Next, suppose that $`𝐠`$ has type $`A_2`$. The canonical basis in this case was also determined by Lusztig . We have

$$\begin{array}{cccc}\hfill 𝐁& =& & \{F_1^{(a)}F_2^{(b)}F_1^{(c)}:a,b,c,ba+c\}\hfill \\ & & & \{F_2^{(a)}F_1^{(b)}F_2^{(c)}:a,b,c,ba+c\}.\hfill \end{array}$$

When $`b=a+c`$ one has the relation

$$F_1^{(a)}F_2^{(a+c)}F_1^{(c)}=F_2^{(c)}F_1^{(a+c)}F_2^{(a)},$$

but apart from this the above elements of $`𝐁`$ are all distinct. Thus in this case each canonical basis element may be written as a monomial in the generators $`F_1,F_2`$. The two types of monomials which arise are related to the two reduced decompositions of the longest element $`w_0`$ of the Weyl group $`W`$ of $`𝐠`$. We have $`W=s_1,s_2`$ and $`w_0=s_1s_2s_1=s_2s_1s_2`$. Each of these reduced words for $`w_0`$ gives rise to a type of monomial in the canonical basis.

We now turn to the case when $`𝐠`$ has type $`A_3`$. Lusztig  obtained many, but not all, elements of $`𝐁`$ as monomials in the generators $`F_1,F_2,F_3`$ and gave an example of an element of $`𝐁`$ which could not be written as a monomial in $`F_1,F_2,F_3`$. The remaining elements of $`𝐁`$ were determined by Xi . In order to describe the monomials in $`𝐁`$ we consider reduced words for $`w_0`$. In type $`A_3`$ $`w_0`$ has $`16`$ reduced expressions. However it is natural to divide them into equivalence classes called commutation classes; two reduced words being equivalent if one can be obtained from the other by a succession of commutations in the Coxeter generators of $`W`$. For example, $`s_1s_3s_2s_1s_3s_2`$ is in the same commutation class as $`s_3s_1s_2s_3s_1s_2`$, where the generators are numbered as in the Dynkin diagram (see Figure $`1`$).

There are $`8`$ commutation classes of reduced words for $`w_0`$ in type $`A_3`$. Each of these gives rise to a family of monomials in $`F_1,F_2,F_3`$ which lie in $`𝐁`$. For example, the reduced word $`w_0=s_1s_3s_2s_1s_3s_2`$ gives rise to monomials

$$F_1^{(a)}F_3^{(b)}F_2^{(c)}F_1^{(d)}F_3^{(e)}F_2^{(f)},a,b,c,d,e,f,$$

and such a monomial was shown by Lusztig to lie in the canonical basis $`𝐁`$ provided

$$ca+d,cb+e,d+ec+f.$$

These inequalities come from considering two consecutive occurrences of a given Coxeter generator $`s_i`$ in the given reduced word. The sum of the exponents corresponding to these occurrences of $`s_i`$ is less than or equal to the sum of the exponents corresponding to Coxeter generators $`s_j`$ between these two occurrences of $`s_i`$ such that $`s_j`$ does not commute with $`s_i`$. Lusztig obtained $`8`$ families of monomials in $`𝐁`$ in this way, and the remaining elements of $`𝐁`$ determined by Xi are linear combinations of monomials with coefficients which are quantum binomial coefficients.

We now suppose that $`𝐠`$ has type $`A_4`$. Here the situation is more involved and has been investigated by the authors. We shall outline the situation in the present paper, and hope to publish the proofs in a subsequent article. For each reduced word $`w_0=s_{i_1}s_{i_2}\mathrm{}s_{i_k},`$ where $`k=\mathrm{}(w_0)`$, we write $`𝐢=(i_1,i_2,\mathrm{},i_k)`$. For each such $`𝐢`$, we define a subset $`C_𝐢`$ of $`^k`$ whose definition is motivated by the rule mentioned above for a monomial to lie in $`𝐁`$ in type $`A_3`$. We define $`C_𝐢`$ to be the set of those $`𝐚^k`$ such that for each pair $`t,t^{}[1,k]`$ with $`t<t^{}`$, $`i_t=i_t^{}`$, $`i_pi_t`$ for $`t<p<t^{}`$, we have $`_pa_pa_t+a_t^{}`$, summed over all $`p`$ with $`t<p<t^{}`$ such that $`s_p`$ does not commute with $`s_{i_t}`$.

The cone $`C_𝐢`$ will be called the Lusztig cone associated with $`𝐢`$. The elements of $`C_𝐢`$ give rise to monomials. Let

$$M_𝐢=\{F_{i_1}^{(a_1)}F_{i_2}^{(a_2)}\mathrm{}F_{i_k}^{(a_k)}:𝐚=(a_1,a_2,\mathrm{},a_k)C_𝐢\}.$$

It was shown by Marsh  that when $`𝐠`$ has type $`A_4`$ we have $`M_𝐢𝐁`$ for each $`𝐢`$. In type $`A_4`$ there are $`62`$ commutation classes of reduced words for $`w_0`$, and we obtain in this way $`62`$ families of monomials in the canonical basis. These are far from being the only elements of $`𝐁`$, however, and the remaining elements are not known as expressions in terms of $`F_1,F_2,F_3,F_4`$.

## 2 PBW-type Bases and the Canonical Basis

We shall now recall Lusztig’s approach to the canonical basis. For each reduced word $`𝐢`$ for $`w_0`$, Lusztig defined  a PBW-type basis $`B_𝐢`$ of $`U_q^{}`$. The reduced word $`w_0=s_{i_1}s_{i_2}\mathrm{}s_{i_k}`$ gives rise to a total order on the set $`\mathrm{\Phi }^+`$ of positive roots of $`𝐠`$. We have

$$\mathrm{\Phi }^+=\{\alpha ^1,\alpha ^2,\mathrm{},\alpha ^k\},$$

where

$$\alpha ^1=\alpha _{i_1},\alpha ^2=s_{i_1}(\alpha _{i_2}),\mathrm{}\alpha ^k=s_{i_1}s_{i_2}\mathrm{}s_{i_{k1}}(\alpha _{i_k}),$$

and $`\alpha _1,\alpha _2,\mathrm{},\alpha _n`$ are the simple roots. By using braid group operations, Lusztig defines for each $`\alpha \mathrm{\Phi }^+`$ a root vector $`F_\alpha U_q^{}`$, beginning with $`F_{\alpha _i}=F_i`$. We write $`F_𝐢^𝐜=F_{\alpha ^1}^{(c_1)}F_{\alpha ^2}^{(c_2)}\mathrm{}F_{\alpha ^k}^{(c_k)}`$ for $`𝐜=(c_1,c_2,\mathrm{},c_k)^k`$. Then the set $`B_𝐢=\{F_𝐢^𝐜:𝐜^k\}`$ is a basis for $`U_q^{}`$, called the PBW-type basis associated to $`𝐢`$.

The lattice $`=[v]B_𝐢`$ was shown by Lusztig to be independent of $`𝐢`$ and there is a bijective map

$`𝐁`$ $``$ $`B_𝐢`$
$`b`$ $``$ $`F_𝐢^𝐜`$
such that $`bF_𝐢^𝐜modv.`$ We write $`\phi _𝐢(b)=𝐜`$. Then the map $`\phi _𝐢:𝐁^k`$ is bijective. This gives, for each $`𝐢`$, a parametrization of $`𝐁`$ by elements of $`^k`$.

Lusztig introduced  two particular reduced words $`𝐣`$, $`𝐣^{}`$ for $`w_0`$. In type $`A_n`$ these are as follows. Suppose the vertices of the Dynkin diagram of $`A_n`$ are labelled as in Figure $`2`$.

Let $`𝐣`$ be $`135\mathrm{}246\mathrm{}135\mathrm{}246\mathrm{}`$, where $`k=\frac{1}{2}n(n+1)`$ factors are taken, and let $`𝐣^{}`$ be $`246\mathrm{}135\mathrm{}246\mathrm{}135\mathrm{}`$, where again $`k`$ factors are taken. Then $`𝐣,𝐣^{}`$ are reduced words for $`w_0`$ and their commutation classes are as far apart as possible, in the sense that they give opposite orderings on $`\mathrm{\Phi }^+`$. Consider the parametrizations $`\phi _𝐣:𝐁^k`$ and $`\phi _𝐣^{}:𝐁^k`$ of $`𝐁`$ corresponding to $`𝐣,𝐣^{}`$ and let $`R=\phi _𝐣^{}\phi _𝐣^1:^k^k`$ be the bijective map which relates them.

The function $`R`$ is the restriction to $`^k`$ of a piecewise-linear map $`R:^k^k`$ and the results in low rank cases suggest that the regions of linearity of $`R`$ are related to the different types of canonical basis elements.

For example, in type $`A_2`$, we have $`𝐣=121`$, $`𝐣^{}=212`$, and $`R`$ has two regions of linearity. These correspond to the two types of monomial in the canonical basis.

In type $`A_3`$, the function $`R`$ has $`10`$ regions of linearity, and $`8`$ of these regions correspond to the $`8`$ families of monomials in the canonical basis. The remaining $`2`$ regions correspond to the remaining non-monomial elements of $`𝐁`$ obtained by Xi. These two regions may be distinguished from the other $`8`$ regions as follows.

In type $`A_3`$, we have $`R:^6^6`$. The $`8`$ regions of linearity of $`R`$ which give rise to monomials in $`𝐁`$ are each defined by $`3`$ inequalities whereas the $`2`$ remaining regions of linearity are each defined by $`4`$ inequalities. This suggests that regions of linearity defined by the minimum number of inequalities might give rise to canonical basis elements of a particularly favourable form.

This turns out to be the case in type $`A_4`$ also. This time we have a piecewise-linear map $`R:^{10}^{10}`$, which was shown by Carter to have 144 regions of linearity. Of these regions, $`62`$ are defined by $`6`$ inequalities, $`70`$ by $`7`$ inequalities, $`10`$ by $`8`$ inequalities, and $`2`$ by $`11`$ inequalities. It is striking that the number of regions defined by the minimum number of inequalities is equal to the number of commutation classes of reduced words for $`w_0`$.

The authors have shown that in type $`A_4`$ there is a natural bijection between commutation classes of reduced words for $`w_0`$ and regions of linearity for $`R`$ defined by the minimum number of inequalities. This comes about as follows. For each reduced word $`𝐢`$ for $`w_0`$ we have a corresponding family $`M_𝐢`$ of monomials in $`𝐁`$, as described above. We consider the set of points in $`^{10}`$ which parametrize these elements of $`𝐁`$ under the map $`\phi _𝐣`$: let $`X_𝐢^+=\phi _𝐣(M_𝐢)`$. Then one can show:
(a) $`X_𝐢^+`$ is the set of all points in a region of linearity $`X_𝐢`$ of $`R`$ with coordinates in $``$.
(b) $`X_𝐢`$ is a region defined by the minimum number of inequalities.
(c) The map $`𝐢X_𝐢`$ is a bijection between commutation classes of reduced words for $`w_0`$ and regions of $`R`$ defined by the minimum number of inequalities.

In fact, both the set of commutation classes of reduced words for $`w_0`$ and the set of regions of $`R`$ defined by the minimum number of inequalities can be given a natural graph structure, and the map $`𝐢X_𝐢`$ is then an isomorphism of graphs.

## 3 Rectangle Calculus

It is natural to ask whether the region $`X_𝐢`$ can be described in terms of $`𝐢`$ without using ideas concerned with the canonical basis, but simply in combinatorial terms. This can be done by a form of combinatorics which we call the rectangle calculus. The basic idea is to associate with the reduced word $`𝐢`$ a set of linearly independent vectors such that $`X_𝐢`$ is the set of all linear combinations of these vectors with non-negative coefficients. These vectors will be called spanning vectors of $`X_𝐢`$.

We first introduce the idea of a partial quiver. This is a Dynkin diagram with arrows on certain edges, such that the set of edges with arrows in non-empty and connected. An example of a partial quiver of type $`A_7`$ is given in Figure $`3`$.

We are concerned with partial quivers of type $`A_n`$, and shall use $`L`$ or $`R`$ to indicate whether an arrow goes left or right. Thus the above partial quiver is denoted $`RLL`$.

The possible partial quivers of type $`A_4`$ are $`LLL`$, $`RLL`$, $`LRL`$, $`LLR`$, $`LRR`$, $`RLR`$, $`RRL`$, $`RRR`$, $`LL`$, $`LL`$, $`LR`$, $`LR`$, $`RL`$, $`RL`$, $`RR`$, $`RR`$, $`L`$, $`L`$, $`L`$, $`R`$, $`R`$, $`R`$.

We shall now explain a procedure by which each reduced word $`𝐢`$ for $`w_0`$ in type $`A_n`$ gives a set of $`\frac{1}{2}n(n1)`$ partial quivers. We first write down the braid diagram of $`𝐢`$. This determines a set of chambers, and for each bounded chamber we write down the corresponding chamber set, which is the subset of $`\{1,2,\mathrm{},n+1\}`$ corresponding to the strings which pass below the chamber. We illustrate this by the example in which $`n=4`$ and $`w_0=s_2s_3s_4s_3s_1s_2s_1s_3s_2s_4`$ — see Figure $`4`$.

Each chamber set obtained in this way is a subset of $`\{1,2,\mathrm{},n+1\}`$ which is not an initial or terminal subset, i.e. not of form $`\{1,2,\mathrm{},i\}`$ or $`\{i,i+1,\mathrm{},n+1\}`$ for any $`i`$.

Let $`𝒮`$ be the set of all subsets of $`\{1,2,\mathrm{},n+1\}`$ which are not initial or terminal subsets and $`𝒫`$ be the set of all partial quivers of type $`A_n`$. We shall describe a bijection from $`𝒮`$ to $`𝒫`$. We first number the edges of the Dynkin diagram as shown in Figure $`5`$.

Thus the edges are numbered $`2,3,\mathrm{},n`$ from right to left and $`1,n+1`$ are regarded as virtual edges.

Let $`S𝒮`$ and $`P`$ be the corresponding partial quiver. $`P`$ is obtained from $`S`$ by the following rules.

(a) If $`1,n+1S`$, the entries in $`S`$ give the edges of type $`L`$ in $`P`$, edges intermediate between those of type $`L`$ having type $`R`$. The leftmost and rightmost labelled edges of $`P`$ have type $`L`$.
(b) Now suppose $`1S`$. Let $`i`$ be such that $`1,2,\mathrm{},iS`$ but $`i+1S`$. Then edge $`i+1`$ is labelled $`R`$ and is the rightmost labelled edge in $`P`$.
(c) Now suppose $`n+1S`$. Let $`i`$ be such that $`i,i+1,\mathrm{},n+1`$ lie in $`S`$ but $`i1S`$. Then edge $`i1`$ of $`P`$ is labelled $`R`$ and is the leftmost labelled edge in $`P`$.
(d) The elements of $`S`$ not in an initial segment as in (b) or a terminal segment as in (c) give rise to edges $`L`$ or $`R`$ in $`P`$ as in (a).

Example.
Let $`n=13`$. If $`S=\{1,2,3,4,7,8,11\}`$, then $`P=LRRLLRR`$. See Figure $`6`$ for an explanatory diagram.

Applying this bijection $`𝒮𝒫`$ to the chamber sets obtained from a reduced word $`𝐢`$ we obtain a set of $`\frac{1}{2}n(n1)`$ partial quivers associated with $`𝐢`$. In the above example with $`n=4`$ and $`w_0=s_2s_3s_4s_3s_1s_2s_1s_3s_2s_4`$ we obtain the partial quivers shown in Figure $`7`$.

We denote by $`𝒫(𝐢)`$ the set of partial quivers obtained from $`𝐢`$ in this way.

We now introduce the rectangles which we shall be considering. Let $`i,j,k,l`$ satisfy:

$$i<j<l,i<k<l,i+l=j+k.$$

An $`(i,j,k,l)`$-rectangle is a rectangle with corners on levels $`i,j,k,l`$. It is most convenient to illustrate this idea by means of an example. See Figure $`8`$.

The sides of the rectangle have gradient $`\pm \pi /4`$. The $`(i,j,k,l)`$-rectangle contains alternate columns of integers starting with the first column if the entry in it is odd and the second column otherwise. See Figure $`9`$.

The columns of integers in the rectangle are interpreted as positive roots; for example the $`(0,2,3,5)`$-rectangle contains roots $`\alpha _1+\alpha _2+\alpha _3,\alpha _2+\alpha _3+\alpha _4`$.

We next describe how each partial quiver determines a configuration of rectangles. It is again most convenient to explain this by means of an example. Consider the case of type $`A_{10}`$ in which we take the partial quiver $`P=LLRRRLRR`$ — see Figure $`10`$.

The edges of the partial quiver are numbered as shown. We first divide the partial quiver into its components, i.e. the maximal subquivers containing a set of consecutive $`L`$’s and $`R`$’s. The components of our given partial quiver $`P`$ are:

$$\begin{array}{ccccccccc}& L& L& & & & & & \\ & & & R& R& R& & & \\ & & & & & & L& & \\ & & & & & & & R& R\end{array}$$

For each component $`K`$ of $`P`$ we define positive integers $`a(K)`$, $`b(K)`$ with $`a(K)<b(K)`$. The integer $`a(K)`$ is the number of the edge following the rightmost arrow of $`K`$ and $`b(K)`$ is the number of the edge preceding the leftmost arrow of $`K`$. In the above example the numbers $`a(K),b(K)`$ are as follows:

$$\begin{array}{cccccccccccccc}& & & & K& & & & & & & a(K)& & b(K)\\ & & & & & & & & & & & & & \\ & L& L& & & & & & & & & 7& & 10\\ & & & R& R& R& & & & & & 4& & 8\\ & & & & & & L& & & & & 3& & 5\\ & & & & & & & R& R& & & 1& & 4\end{array}$$

For each component $`K`$ of type $`L`$ we take a $`(0,a,n+2b,n+ab+2)`$-rectangle and for each component $`K`$ of type $`R`$ we take a $`(ba1,b1,n+1a,n+1)`$-rectangle, where $`a=a(K)`$, $`b=b(K)`$. Thus the $`4`$ components of our partial quiver $`P=LLRRRLRR`$ give the $`4`$ rectangles shown in Figure $`11`$.

We now observe that for a component of type $`L`$ immediately followed by a component of type $`R`$ the two corresponding rectangles fit together from the left hand corner. Also, for a component of type $`R`$ immediately followed by a component of type $`L`$ the two rectangles fit together from the right hand corner. This can be observed in the four rectangles above, in which the first and the second fit from the left, the second and the third from the right, and the third and the fourth from the left.

We use these rules to superimpose the rectangles obtained from the components of the given partial quiver. In the case of the partial quiver $`P=LLRRRLRR`$ we obtain the configuration of rectangles shown in Figure $`12`$.

We next define the centre of such a configuration. First consider the rectangles in the diagonals from north-west to south-east. The number of such rectangles in these diagonals in the above configuration is $`1,3,4,2`$. It is always the case that one obtains a set of odd numbers followed by a set of even numbers or vice versa. We draw the diagonal line separating the diagonal blocks giving odd and even numbers of rectangles. This is the line $`\mathrm{}`$ in Figure $`13`$. A similar phenomenon occurs for the diagonals from northeast to southwest. The number of rectangles in such diagonals in the above configuration is $`2,4,3,1`$ and we draw the diagonal line separating the diagonal blocks giving odd and even numbers of rectangles. This is the line $`\mathrm{}^{}`$ in Figure $`13`$. The point $`O`$ in which $`\mathrm{}`$ and $`\mathrm{}^{}`$ intersect is called the centre of the configuration and we draw in the vertical line through $`O`$, called the central line, $`m`$. See Figure $`13`$.

We consider the left and right hand corner points in this configuration. These are labelled $`A,B,C,D,E`$ in the above example. To each such corner point we associate the rectangle which has the given point as a vertex and whose edges through this point extend as far as possible in the figure. (The vertex of the rectangle opposite to the given corner point may not be explicitly shown in the figure). For each such corner point $`V`$ we define a set of positive roots $`\mathrm{\Phi }^+(V)`$. This is the set of all positive roots in the rectangle associated with $`V`$ on the same side of the central line $`m`$ as $`V`$ itself.

Thus in the given example, we have:

$`\mathrm{\Phi }^+(A)`$ $`=`$ $`\{\alpha _2,\alpha _1+\alpha _2+\alpha _3+\alpha _4,\alpha _3+\alpha _4+\alpha _5+\alpha _6\}`$
$`\mathrm{\Phi }^+(B)`$ $`=`$ $`\{\alpha _7,\alpha _5+\alpha _6+\alpha _7+\alpha _8+\alpha _9\}`$
$`\mathrm{\Phi }^+(C)`$ $`=`$ $`\{\alpha _6+\alpha _7+\alpha _8,\alpha _4+\alpha _5+\alpha _6+\alpha _7+\alpha _8+\alpha _9+\alpha _{10}\}`$
$`\mathrm{\Phi }^+(D)`$ $`=`$ $`\{\alpha _3,\alpha _1+\alpha _2+\alpha _3+\alpha _4+\alpha _5,\alpha _2+\alpha _3+\alpha _4+\alpha _5+\alpha _6+\alpha _7\}`$
$`\mathrm{\Phi }^+(E)`$ $`=`$ $`\{\alpha _{10},\alpha _8+\alpha _9\}`$
We then define $`\mathrm{\Phi }^+(P)`$ to be the union of the sets $`\mathrm{\Phi }^+(V)`$ for all corner points $`V`$ in the configuration. This is always a disjoint union. In the given example we have:

$`\mathrm{\Phi }^+(P)`$ $`=`$ $`\{\alpha _2,\alpha _1+\alpha _2+\alpha _3+\alpha _4,\alpha _3+\alpha _4+\alpha _5+\alpha _6,\alpha _7,\alpha _5+\alpha _6+\alpha _7+\alpha _8+\alpha _9,`$
$`\alpha _6+\alpha _7+\alpha _8,\alpha _4+\alpha _5+\alpha _6+\alpha _7+\alpha _8+\alpha _9+\alpha _{10},\alpha _3,\alpha _1+\alpha _2+\alpha _3+\alpha _4+\alpha _5,`$
$`\alpha _2+\alpha _3+\alpha _4+\alpha _5+\alpha _6+\alpha _7,\alpha _{10},\alpha _8+\alpha _9\}.`$
We now define a vector $`v_P^k`$ whose coordinates are all $`0`$ or $`1`$. Let $`𝐣`$ be the reduced word

$$135\mathrm{}246\mathrm{}135\mathrm{}246\mathrm{},$$

considered above, and let $`\alpha ^1,\alpha ^2,\mathrm{},\alpha ^k`$ be the corresponding order on the set of positive roots. We define $`v_P`$ as the vector whose $`i`$th coordinate is $`1`$ if $`\alpha ^i\mathrm{\Phi }^+(P)`$ and is $`0`$ otherwise. We also define vectors $`v_j^k`$ for $`j=1,2,\mathrm{},n`$, where the $`i`$th component of $`v_j`$ is $`1`$ if the $`i`$th letter in $`𝐣`$ is $`j`$ and is $`0`$ otherwise.

These vectors $`v_P,P𝒫(𝐢)`$ and $`v_j`$, $`j\{1,2,\mathrm{},n\}`$ turn out to be our required spanning vectors for the region $`X_𝐢`$.

###### Proposition 3.1

Suppose that $`𝐠`$ has type $`A_4`$ and let $`𝐣`$ be the reduced word $`1324132413`$ for $`w_0`$. Let $`𝐢`$ be any reduced word for $`w_0`$ and $`𝒫(𝐢)`$ be the set of partial quivers associated with $`𝐢`$. We have $`|𝒫(𝐢)|=6`$. Then the region $`X_𝐢^+`$ associated with $`𝐢`$ is the set of all non-negative integral combinations of the vectors $`v_P,P𝒫(𝐢)`$, and $`v_j`$ for $`1j4`$.

This Proposition explains how the regions $`X_𝐢^+`$ can be described by the rectangle combinatorics.

## 4 Speculations for type $`A_n`$

It is natural to ask whether the set $`X_𝐢`$ defined as the set of non-negative linear combinations of the vectors $`v_P`$, $`P𝒫(𝐢)`$ and $`v_j`$, $`1jn`$ is a region of linearity for $`R:^k^k`$ in type $`A_n`$. No counter-example is known to the authors. If so, are the $`X_𝐢`$ the only regions of linearity of $`R`$ defined by the minimum number of inequalities? This would give a bijection in type $`A_n`$ between commutation classes of reduced words for $`w_0`$ and regions of linearity for $`R`$ defined by the minimum number of inequalities.

The set $`M_𝐢`$ of monomials corresponding to points in the Lusztig cone $`C_𝐢`$ is not in general contained in the canonical basis in type $`A_n`$. It is nevertheless possible to consider a subset of $`𝐁`$ in bijective correspondence with $`C_𝐢`$ by means of Kashiwara’s approach to the canonical basis. Kashiwara  defines certain root operators $`\stackrel{~}{F_𝐢}`$ which lead to a parametrization of the canonical basis $`𝐁`$ for each $`𝐢`$ by a certain subset $`K_𝐢^k`$ which we call the string cone. This gives a bijection

$$\psi _𝐢:𝐁K_𝐢.$$

It has been shown independently by Marsh  and by Premat  that $`C_𝐢K_𝐢`$ for each $`𝐢,`$ i.e. that the Lusztig cone lies in the string cone. Thus we obtain a subset $`\psi _𝐢^1(C_𝐢)𝐁`$. This subset is equal to the set of monomials $`M_𝐢`$ when $`n4`$, but does not consist of monomials in general. Using Lusztig’s parametrization

$$\phi _𝐣:𝐁^k$$

where $`𝐣=135\mathrm{}246\mathrm{}135\mathrm{}246\mathrm{},`$ this subset $`\psi _𝐢^1(C_𝐢)`$ of $`𝐁`$ corresponds to a certain subset of $`^k`$. Let

$$S_𝐢^𝐣:K_𝐢^k$$

be the transition map given by $`S_𝐢^𝐣=\phi _𝐣\psi _𝐢^1`$. It is known that in type $`A_n`$, the images of the spanning vectors of the Lusztig cone $`C_𝐢`$ under $`S_𝐢^𝐣`$ are the vectors $`v_P`$, $`P𝒫(𝐢)`$ and $`v_j`$, $`1jn`$ given by the rectangle combinatorics. This can be proved using a transition function introduced by Berenstein, Fomin and Zelevinsky .

Finally, what can be said about canonical basis elements corresponding under $`\phi _𝐣`$ to regions of linearity of $`R`$ not defined by the minimum number of inequalities? The results of Xi  in type $`A_3`$ are interesting in this respect. In type $`A_3`$, Lusztig’s function $`R:^6^6`$ has $`10`$ regions of linearity, $`8`$ of which are the regions $`X_𝐢`$ for the different commutation classes of reduced words $`𝐢`$ for $`w_0`$. These are all defined by $`3`$ inequalities. The remaining two are defined by $`4`$ inequalities and we denote these by $`X_9`$ and $`X_{10}`$. We now define $`\stackrel{~}{X_𝐢^+}`$ to be the set of points in $`X_𝐢`$ whose coordinates are all real and nonnegative. Thus we have

$$X_𝐢^+\stackrel{~}{X_𝐢^+}X_𝐢$$

and $`X_𝐢^+`$ is the set of integral points in $`\stackrel{~}{X_𝐢^+}`$. We define $`\stackrel{~}{X_9^+}`$ and $`\stackrel{~}{X_{10}^+}`$ similarly. We have additional inequalities defining $`\stackrel{~}{X_𝐢^+}`$ asserting that all coordinates are non-negative, but some of these inequalities will be redundant. In fact each of the $`8`$ regions $`\stackrel{~}{X_𝐢^+}`$ can be defined by $`6`$ inequalities and, for suitable numbering, $`\stackrel{~}{X_9^+}`$ can be defined by $`8`$ inequalities and $`\stackrel{~}{X_{10}^+}`$ by $`9`$ inequalities. The regions $`\stackrel{~}{X_𝐢^+}`$ are called simplicial regions as the number of defining inequalities is equal to the dimension of the ambient space. $`\stackrel{~}{X_9^+}`$ can be written as the union of two simplicial regions, and $`\stackrel{~}{X_{10}^+}`$ as the union of four simplicial regions.

Xi obtains $`8`$ families of monomials in $`𝐁`$, which are parametrized by the integral points in the $`8`$ simplicial regions $`\stackrel{~}{X_𝐢^+}`$. In addition he obtains $`6`$ families of elements in $`𝐁`$ which are not monomials. These are parametrized by the integral points in the two simplicial regions whose union is $`\stackrel{~}{X_9^+}`$ and the four simplicial regions whose union is $`\stackrel{~}{X_{10}^+}`$. The canonical basis elements corresponding to a given region are all of the same type, i.e. they can all be expressed as a linear combination of monomials corresponding to a fixed reduced expression with quantum binomial coefficients and exponents lying on a line segment in $`^6`$.

The authors plan to give the proofs of the results described in this article in a forthcoming paper.


text:
# BIHEP-TH-2000-2 Possibility of a Light Pulse with Speed Greater than c

## Abstract

In two models it is shown that a light pulse propagates from a vacuum into certain media with velocity greater than that of a light in a vacuum (c). By numerical calculation the propagating properties of such a light are given.

Recently L. J. Wang and his collaborators in their experiment  have found that the group velocity of a laser pulse in particularly prepared atomic caesium gas can much exceed that of light in a vacuum (c). Here we will explore the problem from a theoretical piont of view. Many years ago A. Sommerfeld rigorously proved  that the velocity of light pulse can not exceed c in absorption media. We call this conclusion as basic theorem afterwardz. In the following we will first examine why usually the basic theorem holds and in what condition it will be violated. Then two models are proposed, where with precise numerical calculation we will show that the basic theorem is indeed violated. Therefore the properties of light propagating in media of the models are given. We believe that these properties may appears in more realistic models.

Let a light pulse propagating along x axis toward its positive direction in a vacuum $`(x<0)`$, at time t = 0 arriving at x = 0, and then entering into a medium $`(x0)`$ afterwards. At x = 0, the amplitude of the light pulse changes with time t as

$`f(t)=\{\begin{array}{cc}F(t)& t0\\ 0& t<0.\end{array}`$ (3)
Usually f(t) can be rigorously expressed in Fourier integration as

$`f(t)=Re{\displaystyle _0^{\mathrm{}}}A(n)e^{int}𝑑n.`$ (4)
For simplicity suppose there is no reflection of light at x = 0. The amplitude of the light pulse entering into the medium $`(x0)`$ is

$`f(t,x)=Re{\displaystyle _0^{\mathrm{}}}A(n)e^{int+ikx}𝑑n,`$ (5)
where $`k=n\mu (n)/c`$ and $`\mu (n)`$ is the complex refractive index of the medium, which depends on the frequency of incident light (dispersion). In vacuum $`(x<0)`$, the amplitude of the light pulse is

$`g(t,x)`$ $`=`$ $`Re{\displaystyle _0^{\mathrm{}}}A(n)e^{int+inx/c}𝑑n(x<0)`$ (8)
$`=`$ $`f(tx/c)=\{\begin{array}{cc}F(tx/c)& tx/c0\\ 0& tx/c<0.\end{array}`$
The shape of the light pulse propagating in a vacuum does not change because all its Fourier components in (4) propagate with the same velocity c and do not decay. In particular, all these components completely cancel each other in the space-time region $`tx/c<0`$ (or $`\theta =tc/x<1)`$ as long as the light pulse propagates in a vacuum. One may think that such a cancellation may not occur when light pulse propagates in a medium because of dispersion and absorption. But Sommerfeld proved that such cancellation also occurs when light pulse propagates in absorption media, which is just the basic theorem. In his proving Sommerfeld let

$`f(t)=\{\begin{array}{cc}sin\nu t& t0\\ 0& t<0,\end{array}`$ (11)
so that (3) becomes

$`f(t,x)={\displaystyle \frac{1}{2\pi }}Re{\displaystyle _c}e_{/(n\nu )}^{i(ntn\mu (n)x/c)}𝑑n,`$ (12)
where $`\mu (n)`$ is taken as

$`\mu ^2=1+{\displaystyle \frac{a^2}{n_0^22i\rho nn^2}},`$ (13)
which is the Lorentz-Lorenz refraction formula. $`a^2,n_0,\rho `$ are the constants of the medium. $`n_0,\rho `$ represent the characteristic absorption frequency, damping constant of the medium. Usually $`\rho >0`$, light propagating in the medium decays. The integration path c in (6) is shown in Fig.1, which is along the real axis of n from $`+\mathrm{}`$ to $`\mathrm{}`$ through $`n=\nu `$ by a small semicircle in the upper half of the complex plane. $`\mu (n)`$ in (7) has branch pionts:

$`U_{1,2}`$ $`=`$ $`i\rho \pm \sqrt{n_0^2\rho ^2},where\mu =\mathrm{};`$
$`N_{1,2}`$ $`=`$ $`i\rho \pm \sqrt{n_0^2+a^2\rho ^2},where\mu =0.`$
We joing $`U_1`$ to $`N_1`$ and $`U_2`$ to $`N_2`$ by two branch lines, which lie in the lower half of the complex plane, when $`\rho >0`$. Because there is no singularity and branch lines of the integrand of (6) in the upper half plane, one can replace the integration path c by u in Fig.1, which is parallel to the real axis in the upper half plane. When u moves to infinity in the upper half plane, $`\mu 1`$ and when $`tx/c<0`$, then (6) = 0, which is just the basic theorem. But when $`\rho <0`$ (this is our model 1), the branch lines $`U_1N_1`$ and $`U_2N_2`$ lie in the upper half plane and the integration path u is not equivalent to the path c in (6). Now the equivalent path u should be taken as $`u_1+u_2+u_3+u_4`$ in Fig.1. By the same argument above, integration along $`u_1`$ vanishs. Integrations along a pair of $`u_2`$ cancel each other. The remaining integations along $`u_3`$ and $`u_4`$ usually do not vanish because the branch lines lie in them. Therefore when $`\rho <0`$ (model 1), the basic theorem does not hold. In the following we will do numerical integration of (6) to show that the basic theorem is indeed violated and to see what happens. $`\rho <0`$ means propagation of light in the medium is gain-assisted light propagation.

From (6) we get

$`f(t,x)={\displaystyle \frac{1}{2}}Re[ie^{\gamma \omega (\overline{\nu })}]+{\displaystyle \frac{1}{2\pi }}Re{\displaystyle _0^{\mathrm{}}}[e^{\gamma w(z+\overline{\nu })}e^{\gamma w(z+\overline{\nu })}]{\displaystyle \frac{dz}{z}},`$ (14)
where $`\gamma w(\overline{n})=int+in\mu x/c;\gamma =xn_0/c,\overline{n}=n/n_0,\overline{\nu }=\nu /n_0,\overline{a}^2=a^2/n_0^2,\overline{\rho }=\rho /n_0`$, all of them are dimensionless. Let

$`w(z)=X(z)+iY(z).`$ (15)
When $`z>>1`$,

$`X(z)\overline{a}^2\overline{\rho }/z^2,Y(z)z(1\theta )\overline{a}^2/(2z),`$ (16)
where $`\theta =ct/x`$.

In reference , the typical values of parameters are given as

$`n_0=4\times 10^{16}s^1,a^2=1.24n_0^2,\rho =0.07n_0,`$ (17)
where the medium is solid or liquid. For gas $`a^2`$ is about 1.001.

The numerical integration for (8) is difficult when $`\gamma Y(z)`$ becomes very large and hence $`e^{\gamma Y(z)}`$ is a very fast oscillatory function of z. In fact when $`n_0=4\times 10^{16}s^1`$ and $`x=1cm,\gamma =\frac{4}{3}\times 10^6`$ is very large. But if $`\gamma <100`$ for example, i.e., $`x<7.5\times 10^5cm`$, we can do numerical integration of (8) with high precision. Now the integration of (8) is divided into sum of $`_0^R`$ and $`_R^{\mathrm{}}`$. With $`R100`$ for example, fast oscillatory integrand appears in $`_R^{\mathrm{}}`$, when $`z>>1`$. Using (10)

$`Re(e^{\gamma \omega (z)})=e^{\gamma \overline{a}^2\overline{\rho }/z^2}\left\{cos[\gamma z(1\theta )]cos{\displaystyle \frac{\gamma \overline{a}^2}{2z}}+sin[\gamma z(1\theta )]sin{\displaystyle \frac{\gamma \overline{a}^2}{2z}}\right\},`$
where the fast oscillatory factors are seperated in forms of sin and cos functions. Mathematica can do that kind of integration with high precision. As an example, let $`\overline{a}^2=1.24,\overline{\rho }=0.07,\overline{\nu }=10,\gamma =1,\theta =0.98`$ in (8), one may get $`f(t,x)=1.02057\times 10^{13}`$, which should vanish exactly due to the basic theorem $`(\rho >0,\theta <1)`$. Considering the amplidude of incident light pulse is 1, $`10^{13}`$ is a very high accuracy of calculation. Now let $`\overline{\rho }=0.07`$ and other parameters unchanged, $`f(t,x)`$ in (8) is 0.0630255, which is a definite evidence to show that the basic theorem is violated indeed when $`\rho <0`$. Because $`\gamma =xn_0/c,\theta =tc/x,f(t,x)`$ may be looked as a function of $`\gamma `$ and $`\theta ,h(\gamma ,\theta )`$. Let us fix $`\gamma =1`$, i.e., $`x=0.75\times 10^6cm`$, and $`\theta `$ change from (-7) to 4, i.e., the time t from $`7/n_0`$ to $`4/n_0`$, the amplitude of light pulse $`h(1,\theta )`$ in the medium is shown in Fig.2, where $`\overline{a}^2=1.24,\overline{\rho }=0.07,\gamma =1,\overline{\nu }=10(\nu =10n_0)`$. Again when $`\rho <0,h(1,\theta )`$ does not vanish and the basic theorem is violated. In Fig.2 even if $`t<0`$, the amplitude $`h(1,\theta )`$ still does not vanish, which means that before the incident light pulse arrives at the medium, the light in the medium is already produced. For convenience, we call the light produced in the medium when $`\theta <1`$ as fastlight and that when $`\theta >1`$ as normal light. When the basic theorem holds, the fastlight vansishes. Some maximal values of light amplitude near $`\theta =1`$ and their corresponding $`\theta `$ values are listed in table 1, where two characteristics are shown:

(1) The amplitude of fastlight is oscillatory and decays as $`\theta \mathrm{}`$;

(2) The period for each oscillation for $`\theta `$ less and near 1 are roughly around $`\theta =6`$, which means its frequency is near the characteristic frequency $`n_0`$ of the medium (the corresponding period is $`\theta =2\pi )`$. This near equality is due to the fact that the Fourier components of the light pulse having freqencies equal to or near $`n_0`$ are most gain-assisted when $`\rho <0`$. When $`\theta >1`$, the normal light soon oscillates with the frequency $`\nu `$ of the incident light pulse (corresponding period $`\theta =0.2\pi `$) and its amplitude is a little bit lager than 1(1.00089). When $`\overline{\nu }=1`$ with other parameters $`\overline{a}^2=1.24,\overline{\rho }=0.07,\gamma =1`$ unchanged the two properties (1) and (2) remain, but the amplitude of the fastlight increases to 6.14 near $`\theta =1`$. The amplitude of normal light inceases to 7.31 with frequency $`\nu =n_0`$.

Model 2: the $`\rho `$ in (7) depends on frequency n as

$`\rho (n)=\{\begin{array}{cc}\rho _1\hfill & \mathrm{}b<n<\mathrm{}+b\hfill \\ \rho _2\hfill & n\mathrm{}born\mathrm{}+b,\hfill \end{array}`$ (20)
which is not continuous and therefore $`\mu (n)`$ and the integrand in (6) are not the analystic functions of n. We still can use numerical calculation to see whether the basic theorem holds:

(a) $`\overline{a}^2=1.24,\rho _1=0.07,\rho _2=0.07,\mathrm{}=1,b=0.01,\overline{\nu }=1,\gamma =1`$. Now light amplitude in the medium are gain-assisted when $`(1b)n_0<n<(1+b)n_0`$ and decays otherwise. Fastlight with above two properties appears again and its amplitude near $`\theta =1`$ is 3.81, while that of normal light is about 4.5;

(b) $`\rho _1=0.02`$ with other parameters unchanged as in (a). Now light in the whole frequency range in the medium decays. Still fastlight remains with the two properties, but its amplitude becomes small (0.0757) near $`\theta =1`$.

So we may conclude that if $`\mu (n)`$ in (6) is an analystic function of n with singularities (such as poles or branch lines) appearing in the upper half plane of n, or $`\mu (n)`$ is not an analystic function of n at all, the basic theorem in general may not hold and fastlight appears. The Fourier components of a light pulse now will not cancel each other in the medium in the space-time region $`tx/c<0`$. This is why fastlight appears.

How to measure the velocity of the light pulse when fastlight appears in the medium? Suppose a light pulse produced in a source at $`t=0`$, propagating a distance $`\mathrm{}_1`$ in a vacuum, then going through a medium with thickness $`\mathrm{}_2`$. Just after the medium a light pulse detector is put. Usually the fastlight appears in the medium after the light pulse is produced and the amplitude of the fastlight is inceasing when the light pulse is approaching to the medium. If the amplitude of fastlight is able to become large enough to trigger the detector at $`t=t_1`$, one may take $`v=(\mathrm{}_1+\mathrm{}_2)/t_1`$ as the velocity of the light pulse propagating from the source to the detector, which certainly exceeds c.

Although the models proposed above are not completely realistic, we believe that production of the fastlight and some its properties in the models may remain in a more realistic model, which is under investigation now.

We would like to thank professors Gu Yi-fan and Dong Fang-xiao for their beneficial discussion.

Table 1. Some maximal values of light amplitude $`h(1,\theta )`$ near $`\theta =1`$ $`(\overline{a}^2=1.24,\overline{\rho }=0.07,\gamma =1`$ and $`\overline{\nu }=10`$ in model 1)

| $`\theta `$ | -46.86 | -40.70 | -34.57 | -28.44 | -22.35 | -16.29 | -10.27 |
| --- | --- | --- | --- | --- | --- | --- | --- |
| $`h(1,\theta )`$ | 0.00909 | 0.0125 | 0.0172 | 0.0232 | 0.0316 | 0.0413 | 0.0580 |
| -4.59 | 0.8714 | 1.1508 | 1.77912 | 2.40744 | 3.03575 |  | |
| 0.0742 | 0.0635 | 1.0089 | 1.0089 | 1.0089 | 1.0089 |  | |