text:
# Conductivity in quasi two-dimensional systems

## I Introduction

The low temperature conductivity of quasi two-dimensional systems like MOSFET structures or hetero-junctions reveals a surprising metal to insulator transition . This critical review of the theoretical approaches has concluded that this phenomenon is insufficiently explained. The experimental data shows a pronounced transition from insulating behavior at low densities to a metallic behavior at high densities. The generic feature of the metal-insulator transition is the rapid change from insulating to conducting behavior when the density is increased very slightly at low temperatures. This density driven metal-insulator transitions are usually referred to as Mott transitions . The characteristic feature of the Mott-Hubbbard transition is that an increase in the effective mass is directly responsible for increasing resistivity $`\rho =m/e^2n\tau `$ while the Anderson scenario would assume a vanishing relaxation time $`n\tau `$. Measurements of the effective mass  seem to support a Mott-Hubbard transition rather than the Anderson transition quantitatively explained in Ref. .

In this paper we want to return to the original idea of the Mott transition in that a bound state is resolved with increasing density due to pressure ionization. We will show that a quantitative description of the experimental results can be achieved if one calculates the interplay of weak localization and trapping due to charged impurities as well as the scattering with neutral impurities on the same theoretical footing.

Weak localization as a quantum interference effect is intensively studied in the literature . The maximally crossed diagrams lead to a diffusive pole which allows one to extract weak localization corrections to the conductivity  (and citations therein). This paper is devoted to an alternative route to weak localization. We will linearize the quantum kinetic equation derived at a lower level of approximation but with external fields in order to create higher order diagrams. The main aim is to show that weak localization has the same origin as the interference effect known from the Debye -Onsager relaxation effect in plasma physics.

In the following part of the introduction we will outline the model we want to use. This will give a summary about the kinetic approach adopted in this paper. The many-body approximation to be applied in this paper is also specified and it is clarified how higher order diagrams are generated by linearization, which is presented in detail in appendix A. In the second section we calculate the electrical conductivity from the kinetic equation approach and present results for the relaxation time and the relaxation function. This relaxation function summarizes the quantum corrections to the conductivity due to interference effects. The Lenard-Balescu kinetic equation used as a starting point in this section is derived in appendix B. The third section discusses the resulting conductivity formulae and shows that the relaxation function is identical to the one calculated for the weak-localization corrections. For comparison with experiment we include scattering from neutral impurities besides the scattering with charged impurities which are worked out in detail in appendix C. The fourth section summarizes the results and gives an outlook. In appendix D we discuss the polarization function in quasi two-dimensional systems. The additional appendices E and F present calculations of the integrals used during the paper.

### A Outline of the model

As a model, we assume a quasi two-dimensional Coulomb potential, where the field lines are three dimensional but the motions of the particles are restricted to two dimensions. The effective potential takes then the form $`V_{ab}=4\pi e_ae_b\mathrm{}/\sqrt{q_x^2+q_y^2}`$ where for instance $`e_a=e`$ for electrons and $`e_b=Ze`$ for charged ions. Our approach is conveniently based on the kinetic equation for the one-particle distribution $`f_a(k,t)`$ normalized to the area density

$`s{\displaystyle \frac{d𝐤}{(2\pi \mathrm{})^2}f_a(𝐤,t)}=n_a`$ (1)
where the spin degeneracy is denoted by $`s`$. The kinetic equation for that distribution function is

$`_tf_a+e_a𝐄_𝐤f_a={\displaystyle \underset{b}{}}[f_a,f_b,𝐄]`$ (2)
where correlations are covered by the corresponding collision integral $``$. This collision integral is explicitly field dependent due to the distortion of two-particle correlations. We consider the conductivity in a system described by a local equilibrium distribution

$`f_a(𝐤,t)=\left(\mathrm{e}^{\frac{(𝐤𝐩_𝐚(t))^2\mu _a}{2m_aT_a}}+1\right)^1`$ (3)
with the mean mass-motion of the charged particle $`𝐩_𝐚(t)`$. The center of mass motion is at rest, which means that the total sum of currents $`\underset{b}{}𝐣_𝐛=\underset{b}{}\frac{n_b|e_b|𝐩_𝐛}{m_b}=0`$ with density $`n_b`$ and mass $`m_b`$. In the following we will restrict ourselves to a two-component system. The generalization towards multicomponent systems is straightforward.

From the collision integral (2) we have two sources of linear response: A term proportional to the current $`𝐣=e_an_a𝐩_𝐚/m_a`$ and a term proportional to the field. By multiplying (2) with $`k`$ and integrating, the balance equation for the momentum reads

$`_t(n_a𝐩_𝐚)n_ae_a𝐄`$ $`=`$ $`{\displaystyle \frac{dk}{(2\pi \mathrm{})^2}𝐤}`$ (4)
$`=`$ $`n_ae_a𝐄{\displaystyle \frac{\delta E}{E}}+n_a𝐩_𝐚\tau ^1`$ (5)
such that the current balance takes the form

$`_t𝐣_𝐚{\displaystyle \frac{n_ae_a^2}{m_a}}\left(1{\displaystyle \frac{\delta E}{E}}\right)𝐄=\tau ^1𝐣_𝐚`$ (6)
and the stationary conductivity $`𝐣=\sigma 𝐄`$ is

$`\sigma ={\displaystyle \frac{n_ae_a^2}{m_a}}{\displaystyle \frac{1\frac{\delta E}{E}}{\tau ^1}}.`$ (7)
According to the distortion of the Fermi function (3) we have a linear response

$`f_a^{}f_a=𝐩_𝐚\left(_{𝐤_𝐚^{}}_{𝐤_𝐚}\right)f_0`$ (8)
and we can represent the current relaxation time and the relaxation effect for a scattering with impurities (C12) with the potential $`V_s`$ as

$`\left(\begin{array}{c}\frac{1}{\tau _i}\\ \frac{\delta E_i}{E}\end{array}\right)`$ $`=`$ $`{\displaystyle \frac{2n_i}{n_a\mathrm{}}}{\displaystyle \frac{dkdq}{(2\pi \mathrm{})^4}_{ϵ_k}f_0(ϵ_k)V_s^2(q)q^2\mathrm{cos}^2(q,E)}`$ (10)
$`\times \left(\begin{array}{c}\pi \delta (ϵ_kϵ_{kq})\\ \frac{\mathrm{}}{2}\frac{𝒫^{}}{ϵ_kϵ_{kq}}\end{array}\right).`$
The relaxation time $`\tau `$ is coming from the term proportional to the current in the collision integral. This is due to on-shell scattering represented by the delta function in (10). Besides this the conductivity becomes renormalized by the explicit field dependence of the collision integral, $`\frac{\delta E}{E}`$, which is an interference effect and corresponds to an off-shell scattering as expressed by the derivative of the principal value in (10). The latter effect has been the subject of various investigations for nondegenerate plasmas and is known as Debye-Onsager relaxation effect. The field dependence and quantum form is discussed in . For a plasma system this Debye- Onsager relaxation effect  was first derived within the theory of electrolytes . ***Debye derived a limiting law of electrical conductivity  which stated that the external electric field $`E`$ on a single charge $`Z=1`$ is diminished in an electrolyte solution by the amount $`\delta E/E=\frac{\kappa e^2}{6T}`$ where $`e`$ is the elementary charge, $`E`$ the electric field strength, $`T`$ is the temperature of the plasma and $`\kappa `$ is the inverse screening radius of the screening cloud. This law is interpreted as a deceleration force which is caused by the deformed screening cloud surrounding the charge. Later it has been shown by Onsager  that this result has to be corrected to $`\delta E/E=\frac{\kappa e^2}{3(2+\sqrt{2})T}`$ if the dynamics of ions ($`Z=1`$) is considered. The linear response theory reproduce this Onsager result . The kinetic theory leads to the Onsager result if asymmetric screening  is applied while the symmetric treatment leads to the Debye result .

The theoretical calculations of conductivity in reduced dimensions is the topic of intensive investigations. These concern rigid two dimensional electron systems and quasi-two dimensional systems. In the latter study a three-dimensional system was considered, where the particles can only scatter in two dimensions leading to a cylindrical Fermi surface. The Born approximation and contact interaction result in a resistivity which has a leading low temperature behavior as $`\frac{1}{\sigma }aT^2(1+b\mathrm{ln}T)`$. We will show that the Coulomb interaction with the dynamical screening results in a linear order as the leading term. This has been repeatedly reported in the literature both from an experimental and theoretical point of view. Numerical calculations of Coulomb scattering rates from impurities predict a linear temperature dependence of the mobility in silicon inversion layers . This was attributed to the collisional level broadening in the screening function. Related results have been obtained in Ref.  where a significant suppression of the temperature dependence of the screening function was found. An analytical investigation of screening in quasi two-dimensional systems was given in Ref.  where a linear temperature term in the conductivity was reported.

In this paper we want to investigate the effect of Coulomb screening on the conductivity. We will derive exact analytical results which show that due to dynamical screening the leading low temperature contribution to the conductivity is linear. In contrast, the static screening leads to a quadratic temperature dependence typical for the Fermi liquid.

### B Many body approximation used in this paper

For the calculation of the conductivity we want to account for quantum interference effects such like weak localization. This means we have to include maximally crossed diagrams at least . Besides the direct calculation of diagrams, we can employ the philosophy of variational techniques. In Ref.  it was described how one can use the variation of nonequilibrium Green’s functions with respect to an auxiliary external field to create higher order diagrams in the response function. This makes use of the known variation technique summarized in appendix A.

The response function can be given in terms of the particle hole T-matrix which in turn can be represented by the sum of irreducible graphs, $`\mathrm{\Xi }`$, according to figure 1. In turn, $`\mathrm{\Xi }`$ can be expressed as a variation of the selfenergy $`\mathrm{\Sigma }`$ with respect to the Green’s function (bare line) $`G`$. For the dynamical screened approximation used here we give the corresponding results in figure 1. One sees that in principle maximally crossed diagrams are accounted for.

Instead of the variation of the nonequilibrium Green’s function we can use a proper reduction of the latter ones towards a kinetic equation. The linear response obtained from this kinetic equation including all external field effects is accounting then for higher order diagrams in a convenient way. As such, we obtain weak localization effects by proper linearization of the collision integral.

## II Kinetic equation and conductivity

The kinetic equation corresponding to the dynamical screened approximation is the quantum Lenard - Balescu equation, which has been derived for high fields in . A sketch of the derivation is in appendix B

$`{\displaystyle \frac{}{t}}f_a+e𝐄{\displaystyle \frac{}{𝐤_𝐚}}f_a=I_a^{\mathrm{in}}(𝐤,t)I_a^{\mathrm{out}}(𝐤,t).`$ (11)
The collision-in integral is \[$`I^{\mathrm{out}}`$ is given by $`f1f`$ and $`L^<L^>`$\]

$`I_a^{\mathrm{in}}(𝐤,t)=2{\displaystyle \underset{b}{}}s_b{\displaystyle \frac{d𝐪}{(2\pi \mathrm{})^2}V_{ab}^2(𝐪)\underset{0}{\overset{\mathrm{}}{}}𝑑\tau \frac{d\omega }{2\pi }}`$ (12)
$`\times \mathrm{cos}\left[(ϵ_{kq}^aϵ_k^a\mathrm{}\omega ){\displaystyle \frac{\tau }{\mathrm{}}}+{\displaystyle \frac{e_a\mathrm{𝐄𝐪}\tau ^2}{2m_a\mathrm{}}}\right]`$ (13)
$`\times f_a(𝐤𝐪e_a𝐄\tau ,t\tau )(1f_a(𝐤e_a𝐄\tau ,t\tau ))`$ (14)
$`\times {\displaystyle \frac{\mathrm{\Pi }_{bb}^<(𝐪,\omega ,t\frac{1}{2}\tau )}{\left|(𝐪,\omega ,t\frac{1}{2}\tau )\right|^2}}`$ (15)
with the free density fluctuation (B6)

$`\mathrm{\Pi }_{bb}^<(𝐪,\omega ,t)=2{\displaystyle \frac{d𝐩}{(2\pi \mathrm{})^2}\underset{0}{\overset{\mathrm{}}{}}𝑑\tau }`$ (16)
$`\times \mathrm{cos}\left[(\mathrm{}\omega ϵ_p^b+ϵ_{p+q}^b){\displaystyle \frac{\tau }{\mathrm{}}}+{\displaystyle \frac{e_b\mathrm{𝐄𝐪}\tau ^2}{2m_b\mathrm{}}}\right]`$ (17)
$`\times f_b(𝐩+𝐪,t{\displaystyle \frac{1}{2}}\tau )(1f_b(𝐩,t{\displaystyle \frac{1}{2}}\tau )).`$ (18)
Here we use the sum over species explicitly.

The nested form of the Lenard - Balescu collision integral (15) is computationally advantageous. It tells that the collision of particle $`a`$ with momentum $`k`$ on a particle $`b`$ with momentum $`p`$ into $`(a,kq)`$ and $`(b,p+q)`$ can be represented equivalently as a collision of the particle $`a`$ with $`k`$ on a hole $`a`$ with $`kq`$ by a dynamic plasmon emission which is considered as a particle-hole fluctuation of particles $`b`$. For static screening $`(𝐪,0,t)`$, equation (15) reduces to the kinetic equation for statically screened Coulomb potentials in high electric fields (C1) .

Now we calculate the frequency integral in (11) and (15) analytically using the identity (E1). We summarize the result of the frequency integration in the momentum dependent function $`W(q)`$ which takes the explicit form (LABEL:W) for quasi two-dimensional systems.

Performing the balance equation for the current (5) we obtain in linear response the interference term or relaxation function

$`e_an_a{\displaystyle \frac{\delta E}{E}}`$ $`=`$ $`{\displaystyle \frac{2e_a}{m_a\mathrm{}^4}}{\displaystyle \underset{b}{}}s_b{\displaystyle \frac{dq}{(2\pi \mathrm{})^2}W(q)q^2\mathrm{cos}^2(q,E)}`$ (20)
$`\times {\displaystyle \underset{0}{\overset{\mathrm{}}{}}}d\tau \tau ^2I_s(a,\tau )({\displaystyle \frac{1}{2}}\mathrm{\Pi }_{bb}^<(q,0))(ab)`$
and the relaxation time as

$`\tau ^1={\displaystyle \underset{b}{}}\left(R(a,b){\displaystyle \frac{e_am_b}{e_bm_a}}R(b,a)\right)`$ (22)
with

$`n_aR(a,b)`$ $`=`$ $`{\displaystyle \frac{4s_b}{m_a\mathrm{}^4}}{\displaystyle \frac{dq}{(2\pi \mathrm{})^2}W(q)q^2\mathrm{cos}^2(q,E)}`$ (24)
$`\times {\displaystyle \underset{0}{\overset{\mathrm{}}{}}}d\tau \tau I_s(a,\tau )({\displaystyle \frac{1}{2}}\mathrm{\Pi }_{bb}^<(q,0)).`$
Here the static free density fluctuation reads

$`\mathrm{\Pi }_{bb}^>(q,0)`$ $`=`$ $`\mathrm{\Pi }_{bb}^<(q,0)`$ (26)
$`=`$ $`2\pi {\displaystyle \frac{dq}{(2\pi \mathrm{})^2}f_p^b(1f_p^b)\delta (ϵ_pϵ_{p+q})}`$ (27)
and the integral

$`I_s(a,\tau )`$ $`=`$ $`{\displaystyle \frac{dk}{(2\pi \mathrm{})^2}f_a(k)(1f_a(kq))}`$ (30)
$`\times \mathrm{sin}\left(ϵ_{kq}ϵ_k\right){\displaystyle \frac{\tau }{\mathrm{}}}`$
will be calculated in appendix F.

We remark that the interference effect (LABEL:relaxf) vanishes for identical scattering partners, e.g. electron-electron correlations.

When calculating the explicit form of the relaxation time and relaxation function we employ charge neutrality $`e_an_a+e_bn_b=0`$ and restrict ourselves to the case of single charge ions $`e_b=e`$. The case of higher charged ions is also available but is more involved. The generalization to systems with additional particles species is straight forward.

#### 1 Relaxation time by charged impurities

Introducing the dimensionless integration variable $`q=2p_{fa}y`$ we obtain the relaxation time to lowest order in temperature

$`\tau ^1`$ $`=`$ $`{\displaystyle \underset{b}{}}{\displaystyle \frac{m_ae_a^2p_{fa}s_b}{\pi \mathrm{}^4n_a}}\kappa _a\left(T_b{\displaystyle \frac{e_an_aT_a}{e_bn_b}}\right)`$ (32)
$`\times {\displaystyle \frac{\xi }{\xi +1}}{\displaystyle \underset{0}{\overset{1}{}}}𝑑y{\displaystyle \frac{y\kappa _a}{(y+\kappa _a)}}{\displaystyle \frac{1}{\sqrt{1y^2}}}`$
where we have introduced the abbreviation $`\xi =\frac{m_b^2e_b^2}{m_a^2e_a^2}`$. Since the momentum integration $`y1`$ is restricted by the low temperature expansions to values below $`2p_{fa}`$ the low temperature expansion of the inverse screening length (LABEL:kq) becomes a constant

$`\kappa `$ $`=`$ $`{\displaystyle \underset{c}{}}2\pi e_c^2_\mu n_c`$ (33)
$`=`$ $`{\displaystyle \frac{e_a^2m_as_a}{\mathrm{}^2}}\left(1+\left|{\displaystyle \frac{e_bs_b}{e_as_a}}\right|\sqrt{\xi }\right).`$ (34)
We distinguish here between the temperature of electrons $`T_a`$ and the temperature of the ions $`T_b`$ which could mime nonequilibrium effects.

The integral in (32) can be easily calculated

$`R=\tau _{ab}^1`$ $`{\displaystyle \frac{m_a}{n_ae_a^2}}{\displaystyle \frac{e_a^2}{h}}={\displaystyle \frac{8s_b}{s_a^3}}\left({\displaystyle \frac{T_a}{ϵ_{fa}}}+{\displaystyle \frac{T_b}{ϵ_{fa}}}\right){\displaystyle \frac{\xi }{1+\xi }}\kappa _a^{}\kappa _a`$ (36)
$`\times \left({\displaystyle \frac{\pi }{2}}+{\displaystyle \frac{\kappa _a^{}}{\sqrt{1\kappa _a^2}}}\mathrm{ln}{\displaystyle \frac{\kappa _a^{}}{(1+\sqrt{1\kappa _a^2})}}\right)`$
where we will use the abbreviation

$`\kappa _a={\displaystyle \frac{\mathrm{}\kappa }{2p_{fa}}}={\displaystyle \frac{e_a^2m_as_a}{2\mathrm{}p_{fa}}}=\sqrt{{\displaystyle \frac{s_a^3e_a^4m_a^2}{16\pi \mathrm{}^4n_a}}}\sqrt{{\displaystyle \frac{\mathrm{}}{\tau _0ϵ_f}}}`$ (37)
with$`\tau _0^1=me^4s^2/8/\mathrm{}^3`$ during the paper. Furthermore, we distinguish in (37) between the inverse screening length where ions are included, $`\kappa _a^{}`$, and where they are neglected $`\kappa _a`$

$`\kappa _a^{}`$ $`=`$ $`\kappa _a(1+\sqrt{\xi }{\displaystyle \frac{s_b}{s_a}}).`$ (38)
We expand the above result for large and small $`\kappa _a`$ which corresponds also to the small and large density limits

$`R`$ $`=`$ $`{\displaystyle \frac{8s_b}{s_a^3}}\left({\displaystyle \frac{T_a}{ϵ_{fa}}}+{\displaystyle \frac{T_b}{ϵ_{fa}}}\right){\displaystyle \frac{\xi }{1+\xi }}\kappa _a`$ (40)
$`\times \{\begin{array}{c}1\frac{\pi }{4\kappa _a^{}}+\frac{2}{3\kappa _a^2}+o(\kappa _a^3)\\ \\ \frac{\pi }{2}\kappa _a+\kappa _a^2\mathrm{ln}\frac{\kappa _a}{2}+o(\kappa _a^3)\end{array}.`$
It is interesting to investigate the limit of large ion masses, $`\xi \mathrm{}`$ and $`T_b=0`$, which would correspond to the charged impurity limit. One gets from (40) for large $`\kappa _a`$

$`R`$ $`=`$ $`{\displaystyle \frac{8s_b}{s_a^3}}{\displaystyle \frac{T_a}{ϵ_{fa}}}\kappa _a.`$ (41)
If we compare this with the neutral electron-impurity scattering result (LABEL:til), we see significant differences. While the statically screened result shows a Fermi-liquid behavior of $`const`$ and $`T^2`$ terms, the dynamically screened result (41) leads to a linear temperature dependence.

#### 2 Relaxation function by charged impurities

Interference effects from the relaxation function (LABEL:relaxf) can be calculated analogously

$`{\displaystyle \frac{\delta E}{E}}={\displaystyle \frac{e_am_a^2s_b}{2\pi p_{fa}\mathrm{}^3n_a}}\left(e_bT_ae_aT_b\right){\displaystyle \frac{\xi }{\xi +1}}`$ (42)
$`\times {\displaystyle \underset{0}{\overset{\mathrm{}}{}}}dy{\displaystyle \frac{\kappa _a^{}}{y(y+\kappa _a^{})}}_y^2\sqrt{y^21}\mathrm{\Theta }(y1\pm \eta )`$ (43)
The small $`\eta `$ has been introduced to perform the principal value integration $`𝒫`$ according to (F30). It should be noted that the $`\mathrm{\Theta }`$ functions of the denominator and numerator cancel exactly and no restriction on $`y`$-integration remains.

We have now to carefully consider the structure

$`_\pm ={\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑yf_y{\displaystyle \frac{^2}{y^2}}\left[g_y\mathrm{\Theta }(y1\pm \eta )\right]=`$ (44)
$`\times \underset{\eta 0}{lim}({\displaystyle \underset{1\eta }{\overset{\mathrm{}}{}}}dyf_yg_y^{\prime \prime }+(f_yg_y^{}f_y^{}g_y)|_{y=1\eta })`$ (45)
with $`f_y=\kappa _a^{}/y/(y+\kappa _a)`$ and $`g_y=\sqrt{y^21}`$. Performing the integral one sees that the divergent contribution at $`\eta 0`$ is cancelled exactly by the $`fg^{}f^{}g`$ term. We obtain

$`_\pm ={\displaystyle \frac{\kappa _a^{}}{1\kappa _a^2}}\pm {\displaystyle \frac{\pi }{2}}+{\displaystyle \frac{\mathrm{arcosh}\kappa _a^{}}{(\kappa _a^21)^{3/2}}}.`$ (46)
The principal value in (32) is calculated from $`(_++_{})/2`$ and we obtain (with charge $`e_b=e_a`$)

$`{\displaystyle \frac{\delta E}{E}}`$ $`=`$ $`{\displaystyle \frac{2s_b}{s_a^2}}\left({\displaystyle \frac{T_a}{ϵ_{fa}}}+{\displaystyle \frac{T_b}{ϵ_{fa}}}\right)\kappa _a{\displaystyle \frac{\xi }{1+\xi }}`$ (48)
$`\times \left({\displaystyle \frac{\kappa _a^{}}{1\kappa _a^2}}+{\displaystyle \frac{\mathrm{arcosh}\kappa _a^{}}{(\kappa _a^21)^{3/2}}}\right).`$
The low density (large $`\kappa _a`$) expansion as well as the high density (small $`\kappa _a`$) expansion read It is clear that for the impurity limit with infinite masses $`\xi \mathrm{}`$ we have from (38) and (LABEL:el)    $`\left({\displaystyle \frac{\delta E}{E}}\right)_i`$ $`=`$ $`0`$  (50) in agreement with the physical picture that if the ions cannot move the screening cloud cannot deform during the motion of the electrons and cannot induce a relaxation effect. This is different if the charged impurities do not contribute to the screening, $`\kappa _a=\kappa _a^{}`$ in (38), and we obtain a finite result. This case is anticipated here since the neutral static relaxation function already lead to finite results (C35).

$`{\displaystyle \frac{\delta E}{E}}`$ $`=`$ $`{\displaystyle \frac{2s_b}{s_a^2}}\left({\displaystyle \frac{T_a}{ϵ_{fa}}}+{\displaystyle \frac{T_b}{ϵ_{fa}}}\right)\kappa _a{\displaystyle \frac{\xi }{1+\xi }}`$ (52)
$`\times \{\begin{array}{c}\frac{1}{\kappa _a^{}}+\left(\mathrm{ln}(2\kappa _a^{})1\right)\frac{1}{\kappa _a^3}+o(\kappa _a^4)\\ \\ \frac{\pi }{2}+2\kappa _a^{}\frac{3\pi }{4}\kappa _a^2+o(\kappa _a^3)\end{array}.`$
## III Discussion

For further progress we use the expansions for large $`\kappa _a`$ or low densities. Collecting equations (40) and (LABEL:el) we obtain the conductivity in an analogous form to the Bloch-Grüneisen formulae

$`\sigma ={\displaystyle \frac{e^2}{h}}{\displaystyle \frac{1\frac{\delta E}{E}(n)}{R(n)}}`$ (54)
where the dynamic parts comes from the scattering from charged impurities (40), (LABEL:el)

$`R`$ $`=`$ $`{\displaystyle \frac{8s_b}{s_a^3}}\left({\displaystyle \frac{T_a}{ϵ_{fa}}}+{\displaystyle \frac{T_b}{ϵ_{fa}}}\right)\kappa _a\left(1{\displaystyle \frac{\pi }{4\kappa _a}}+{\displaystyle \frac{2}{3\kappa _a^2}}+o(\kappa _a^3)\right)`$ (55)
$`{\displaystyle \frac{\delta E}{E}}`$ $`=`$ $`{\displaystyle \frac{2s_b}{s_a^2}}\left({\displaystyle \frac{T_a}{ϵ_{fa}}}+{\displaystyle \frac{T_b}{ϵ_{fa}}}\right)\left(1\left(\mathrm{ln}(2\kappa _a)1\right){\displaystyle \frac{1}{\kappa _a^2}}+o(\kappa _a^4)\right).`$ (56)
We find that both the relaxation time as well as the relaxation function have a linear temperature dependence for temperatures lower than the Fermi energy. This is in agreement with the experimental and theoretical works mentioned in the introduction.

### A Relation to weak localization

The low density or weak potential limit (54) is now interesting to discuss. Using (37) we can rewrite (54) into a net relaxation effect \[$`s_a=s_b=2`$, $`T_a=T_b`$\]

$`{\displaystyle \frac{\sigma }{\sigma _0}}`$ $`=`$ $`1{\displaystyle \frac{\delta E}{E}}`$ (58)
$`=`$ $`12{\displaystyle \frac{T}{ϵ_f}}\left(1+{\displaystyle \frac{\tau _0ϵ_f}{2\mathrm{}}}\mathrm{ln}\left({\displaystyle \frac{\tau _0ϵ_f}{4\mathrm{}}}\right)\right)`$ (59)
$`=`$ $`12{\displaystyle \frac{T}{ϵ_f}}{\displaystyle \frac{\mathrm{}}{\tau ϵ_f}}\mathrm{ln}\left({\displaystyle \frac{\mathrm{}}{4\tau T}}\right)`$ (60)
where we have introduced the temperature dependent relaxation time $`1/\tau =ϵ_fT\tau _0/\mathrm{}^2=8ϵ_f\mathrm{}T/me^4s^2`$. This is precisely the localization correction to the conductivity . Therefore we understand now the physical meaning of the relaxation function at low temperatures. Please note that it vanishes here for small temperatures in contrast to the static result (C35).

### B Comparison with experiments

In order to describe realistic experiments, we extend our model with scattering from static neutral impurities (treated in appendix C35). In addition to (54) we have static contributions coming from the scattering from neutral impurities (LABEL:til),(C35) as

$`R_i`$ $`=`$ $`{\displaystyle \frac{2^{3/2}s_in_i}{s_an_a}}\left({\displaystyle \frac{a_0}{2r_0}}\right)^2\left\{1{\displaystyle \frac{\pi }{2\kappa _i}}{\displaystyle \frac{\pi ^2}{24}}{\displaystyle \frac{T^2}{e_{fa}^2}}{\displaystyle \frac{\pi ^3}{16\kappa _i}}+o(\kappa _i^4)\right\}`$ (61)
$`{\displaystyle \frac{\delta E_i}{\delta E}}`$ $`=`$ $`{\displaystyle \frac{n_i}{n_a}}\left({\displaystyle \frac{a_0}{2r_0}}\right)^2\left\{1+{\displaystyle \frac{43\mathrm{ln}2\kappa _i}{\kappa _i^2}}+o(\kappa _i^4)\right\}`$ (62)
We can safely use the large $`\kappa _a`$ limit since typical densities of  are $`7\times 10^{10}`$cm-2 and we have

$`\kappa _a={\displaystyle \frac{284.9}{\sqrt{n_a/7\times 10^{10}\mathrm{cm}^2}}}{\displaystyle \frac{m^{}}{m}}`$ (63)
which is a large parameter.

Now we have two unknown fit parameters in the theory. These are the energy level $`E_b=E_cE_D`$ of the impurities determining the ratio of impurity density to electron densities

$`{\displaystyle \frac{n_i}{n_a}}=n_a\left({\displaystyle \frac{2\pi \mathrm{}^2}{m_aT}}\right)\mathrm{e}^{\beta E_b}`$ (64)
and the ratio of the scattering length to the scattering range of neutral impurities $`\zeta =\left(\frac{a_0}{r_0}\right)^2ϵ_{fa}`$. From (54) we can write the final conductivity formula in the form

$`{\displaystyle \frac{\sigma }{\sigma _0}}`$ $`=`$ $`1{\displaystyle \frac{\zeta }{2T}}\mathrm{e}^{E_b/T}{\displaystyle \frac{T}{2ϵ_{fa}}}+{\displaystyle \frac{T}{2ϵ_{fa}\kappa _a^2}}\mathrm{ln}{\displaystyle \frac{2\kappa _a}{e}}`$ (65)
$`\sigma _0`$ $`=`$ $`{\displaystyle \frac{e^2}{h}}\left({\displaystyle \frac{\zeta }{\sqrt{2}T}}\mathrm{e}^{E_b/T}+{\displaystyle \frac{T}{ϵ_{fa}}}\left(\kappa _a{\displaystyle \frac{\pi }{4}}\right)\right)`$ (66)
where we have used the spin degeneracy of the heavy impurities $`s_b=1`$ and the temperature $`T_b=0`$. The best fits to the experimental results  are plotted in figure 2.

We see in figure 2 a clear insulator to metal transition for low temperatures when the density is increased very slightly. The fitting formula (66) works quite well at all experimental densities for low temperatures, however the formula fails for higher temperatures. This is because we used the low temperature Sommerfeld expansion and the Fermi energy is $`1.9`$ K $`\times n_a/7\times 10^{10}cm^2`$ in this case, such that at $`0.8`$K we expect deviations from the leading low temperature behavior. Despite this imperfect agreement with the data, it is quite satisfying that the metal to insulating transition can be described completely by the scattering with charged and neutral donor impurities supplemented by a mass action law. This strongly favors the Mott-Hubbard transition picture.

The best fit parameter are shown in figure 3. We see that the effective binding energy of the electrons to the impurities as well as the scattering strength decrease rapidly when passing through the critical density. This is in agreement with the picture that we have pressure ionization i.e. a crossing between continuum and bound state levels. Therefore, this underlines the Hubbard-Mott transition which we have seen already in the increase of the effective mass  as described in .

A remark concerning the formula (66) should be made here. Instead of the trapping at charged impurities resulting in the mass action law (64), one could assume in principle any other trapping mechanism. In particular, we have shown that three-particle bound states can describe the experimental data as well . The underlying conductivity formula is precisely (66) where the number of three-particle bound states diminishes the charged impurity density correspondingly. So the basic transport mechanisms outlined in this paper here remain the same. The only mechanism that is not possible to extract so far is that of actual trapping.

## IV Summary and Outlook

Linearizing the Lenard - Balescu collision integral including all external field dependences allows one to derive a conductivity on the level of an infinite series of diagrams including maximally crossed lines. The field dependence of the collision integral yields an interference effect which is shown to describe just the weak localization corrections. This has the same formal origin as the Debye-Onsager relaxation effect in plasma and electrolyte systems.

For the low temperature regime, it was possible to calculate the conductivity analytically. It was found that the dynamical screening by charged impurities leads to a linear temperature dependence of the conductivity, while neutral impurities give rise to the usual Fermi liquid behavior. This finding is general for any scattering of light particles from heavy particles. Therefore it might also be of use for scattering rates in high $`T_c`$ cuprates .

The comparison with experiment is performed assuming an appropriate mass action law between the charged donor impurities and the neutral ones which are considered to be captured electrons. The experimental metal-insulator transition can be described quantitatively by fitting the effective binding energy and the unknown scattering strength.

As noted, a similar quality of description of the experimental data was achieved assuming a three particle clustering instead of trapping of electrons. The latter process, however, relies on the same transport picture as outlined in this paper. Only the composition of neutral and charged impurities is determined differently. So far we cannot determine which process is actually happening. In order to achieve this we must study the magnetic field dependence, which shows quite unique and remarkable features in the experiment. This is left for further work.

To conclude, we suggest that the metal insulator transition found in experiments can be described within a Mott-Hubbard transition scenario in agreement with the effective mass measurements .

###### Acknowledgements.

Many discussions with Peter Fulde, James Peter Hague, Rajesh Narayanan, Debanand Sa and Nicolas Shannon are gratefully acknowledged. To Enver Nakhmedov I am especially indebted for suggesting to me the problem of metal to insulator transition.

## A Variational technique of linear response

Assuming besides the interaction potential $`V_{11^{}}`$ also a coupling of an external potential $`U_{11^{}}`$ where the numbers sign cumulative indices like space time,… coordinates, we can express the two particle Green function $`G_{121^{}2^{}}=1/i^2<Ta_1a_2a_2^+a_1^+>`$ by a variation of the one particle Green function $`G_{12}=1/i<Ta_1a_2^+>`$ with respect to the external potential  as

$`G_{121^{}2^{}}=G_{11^{}}G_{22^{}}{\displaystyle \frac{\delta G_{11^{}}}{\delta U_{2^{}2}}}`$ (A1)
where the upper sign denotes the Fermi and the lower the Bose functions. Using the Dyson equation

$`G^1=G_0^1\mathrm{\Sigma }U`$ (A2)
we can calculate the derivative in (A1) and with the help of the chain rule and $`\delta G=G\delta G^1G`$, one can express the fluctuation function as

$`L_{121^{}2^{}}`$ $`=`$ $`G_{121^{}2^{}}G_{11^{}}G_{22^{}}`$ (A3)
$`=`$ $`G_{12^{}}G_{21^{}}G_{13}{\displaystyle \frac{\delta \mathrm{\Sigma }_{34}}{\delta U_{2^{}2}}}G_{41^{}}`$ (A4)
$`=`$ $`G_{12^{}}G_{21^{}}+G_{13}{\displaystyle \frac{\delta \mathrm{\Sigma }_{34}}{\delta G_{56}}}L_{5262^{}}G_{41^{}}.`$ (A5)
Double occurring indices are understood as integrated over. With the definition of the occurring vertex function we can express this graphically

Sometimes it is of advantage to express this density fluctuation function by the T-matrix. Defining

we can express

With the help of (A1), the density response to an external potential can be expressed in terms of the density fluctuation function $`L`$ of (A5). Therefore we remark that the density is given by $`iG_{11^+}=<a_1^+a_1>=<\widehat{n}_1>=n_1`$ and we have from (A1) and (A5) for the response function $`\chi `$

$`\chi _{12}={\displaystyle \frac{\delta n_1}{\delta U_{22}}}=iL_{121^+2}=\pm i<(\widehat{n}_1n_1)(\widehat{n}_2n_2)>.`$ (A6)
The last identity follows from the definition of $`L`$ and underlines the names density fluctuation function. We see now that the linear density variation due to an external potential can be expressed as

$`{\displaystyle \frac{1}{i}}n_1^1=L_{121^+2^+}^0U_2={\displaystyle \frac{1}{i}}\chi _{12}U_{22}`$ (A7)
where the upper index indicates the order of external field dependence. Graphically we can express it as

where we will design the external field as a dotted line ending with a cross. According to (A7) and figure 7 we can express the first order response function as

where we have used the definition of the T-matrix in the u-channel figure 5. The figures (4), (5) and (8) constitutes the approximation used in this paper (1).

## B Dynamical screened approximation in nonequilibrium

The selfenergy is given in terms of the dynamical potential $`𝒱`$ according to figure 1

$`\mathrm{\Sigma }_a^<(𝐤,t,t^{})={\displaystyle \frac{d𝐪}{(2\pi \mathrm{})^2}𝒱_{aa}^<(𝐪,t,t^{})G_a^<(𝐤𝐪,t,t^{})}`$ (B1)
where the dynamical potential is expressed within Coulomb potentials $`V_{ab}(𝐪)`$

$`𝒱_{aa}^<(𝐪,t,t^{})={\displaystyle \underset{dc}{}}V_{ad}(𝐪)_{dc}^<(𝐪,t,t^{})V_{ca}(𝐪)`$ (B3)
via the density-density fluctuation

$`_{ab}^<(𝐪,t,t^{})=\delta _{ab}{\displaystyle 𝑑\overline{t}𝑑\overline{\overline{t}}}`$ (B4)
$`\times \left(^r\right)^1(𝐪,t,\overline{t})\mathrm{\Pi }_{aa}^<(𝐪,\overline{t},\overline{\overline{t}})\left(^a\right)^1(𝐪,\overline{\overline{t}},t^{}).`$ (B5)
Here $`\mathrm{\Pi }`$ is the free density fluctuation or polarization function

$`\mathrm{\Pi }_{aa}^<(𝐪,t,t^{})={\displaystyle \frac{d𝐩}{(2\pi \mathrm{})^2}G_a^<(𝐩,t,t^{})G_a^>(𝐩𝐪,t^{},t)}`$ (B6)
and $`^{r/a}`$ the retarded/ advanced dielectric function

$`^{r/a}(𝐪,t,t^{})=\delta (tt^{})\pm i\mathrm{\Theta }[\pm (tt^{})]{\displaystyle \underset{b}{}}V_{bb}(𝐪)`$ (B8)
$`\times (\mathrm{\Pi }^>(𝐪,t,t^{})\mathrm{\Pi }^<(𝐪,t,t^{})).`$ (B9)
One easily convince oneself that this set of equations (B1-B9) is gauge invariant. The correlation or Green’s function can be related to the Wigner distribution $`f_a`$ by the GKB ansatz

$`G^<(𝐤,\tau ,t)=\mathrm{exp}\left\{{\displaystyle \frac{i}{\mathrm{}}}\left(ϵ_k\tau +{\displaystyle \frac{e^2E^2}{24m}}\tau ^3\right)\right\}`$ (B10)
$`\times f(𝐤{\displaystyle \frac{e𝐄|\tau |}{2}},t{\displaystyle \frac{|\tau |}{2}})`$ (B11)
and analogously for $`G^>`$ by replacing $`f(1f)`$.

With the help of the gauge invariant formulation of Green’s function, we can write the kinetic equation for the Wigner function $`f(𝐩,t)=G^<(𝐩,𝐑,t,\tau =0)`$ finally

$`{\displaystyle \frac{}{t}}f(𝐤,t)+e𝐄_𝐤f(𝐤,t)={\displaystyle \underset{0}{\overset{tt_0}{}}}𝑑\tau `$ (B12)
$`[\{G^>(𝐤{\displaystyle \frac{e𝐄}{2}}\tau ,\tau ,t{\displaystyle \frac{\tau }{2}}),\mathrm{\Sigma }^<(𝐤{\displaystyle \frac{e𝐄}{2}}\tau ,\tau ,t{\displaystyle \frac{\tau }{2}})\}_+`$ (B13)
$`\{G^<(𝐤{\displaystyle \frac{e𝐄}{2}}\tau ,\tau ,t{\displaystyle \frac{\tau }{2}}),\mathrm{\Sigma }^>(𝐤{\displaystyle \frac{e𝐄}{2}}\tau ,\tau ,t{\displaystyle \frac{\tau }{2}})\}_+].`$ (B14)
This kinetic equation is exact in time convolutions. This is necessary because gradient expansions in time are connected with linearization in electric fields and consequently fail . The gradient approximation in space has been applied assuming slow varying processes in space and we have dropped all R-dependence for simplicity. Introducing (B1) into the equation for the Wigner function (B12) one obtains the kinetic equation (11) with the explicit form of collision integral (15).

## C Statically screened or finite range impurity scattering

Using the static approximation for the dielectric function $`(𝐪,0,t)`$ in (15), the kinetic equation for statically screened Coulomb potentials in high electric fields appears

$`{\displaystyle \frac{}{t}}f_a+e𝐄{\displaystyle \frac{}{𝐤_𝐚}}f_a={\displaystyle \underset{b}{}}I_{ab}`$ (C1)
$`I_{ab}={\displaystyle \frac{2s_b}{\mathrm{}^2}}{\displaystyle \frac{d𝐤_𝐚^{}d𝐤_𝐛d𝐤_𝐛^{}}{(2\pi \mathrm{})^4}\delta \left(𝐤_𝐚+𝐤_𝐛𝐤_𝐚^{}𝐤_𝐛^{}\right)}`$ (C2)
$`\times V_s^2(𝐤_𝐚𝐤_𝐚^{},t){\displaystyle \underset{0}{\overset{\mathrm{}}{}}}d\tau \mathrm{cos}\{(ϵ_a+ϵ_bϵ_a^{}ϵ_b^{}){\displaystyle \frac{\tau }{\mathrm{}}}`$ (C3)
$`{\displaystyle \frac{𝐄\tau ^2}{2\mathrm{}}}({\displaystyle \frac{e_a𝐤_𝐚}{m_a}}+{\displaystyle \frac{e_b𝐤_𝐛}{m_b}}{\displaystyle \frac{e_a𝐤_𝐚^{}}{m_a}}{\displaystyle \frac{e_b𝐤_𝐛^{}}{m_b}})\}`$ (C4)
$`\times \left\{f_a^{}f_b^{}(1f_a)(1f_b)f_af_b(1f_a^{})(1f_b^{})\right\}`$ (C5)
describing the scattering of particles $`a`$ (electrons) with other species $`b`$ with the distribution function $`f_b=f_b(k_be_bE\tau ,T\tau )`$. The potential turns out to be the static Debye one

$`V_s(q)={\displaystyle \frac{2\pi e_ae_b\mathrm{}}{(q+\mathrm{}\kappa )}}`$ (C7)
with the static screening length $`\kappa `$ given by

$`\kappa ={\displaystyle \underset{c}{}}2\pi e_c^2_\mu n_c`$ (C8)
and the chemical potential $`\mu `$.

We will now use this statically screened result in order to describe the scattering neutral impurities if we use the range of potential $`r_0=1/\kappa `$ and replace the charges by the scattering strength $`g_{ab}=e_ae_b`$.

The calculation of the impurity scattering in quasi-two dimensions is now analogously to the Brooks-Hearing result for three dimension and starts from the Born collision integral (C1) which takes for infinite heavy ions \[$`m_b/m_a]\mathrm{}`$\]

$`I_{ab}(k_a)={\displaystyle \frac{2s_b}{\mathrm{}^2}}{\displaystyle \frac{d𝐤_𝐚^{}d𝐤_𝐛d𝐤_𝐛^{}}{(2\pi \mathrm{})^4}\delta \left(𝐤_𝐛𝐤_𝐛^{}\right)V_s^2(𝐤_𝐚𝐤_𝐚^{},t)}`$ (C9)
$`\times {\displaystyle \underset{0}{\overset{\mathrm{}}{}}}d\tau \mathrm{cos}\{(ϵ_aϵ_a^{}){\displaystyle \frac{\tau }{\mathrm{}}}{\displaystyle \frac{𝐄\tau ^2}{2\mathrm{}}}({\displaystyle \frac{e_a𝐤_𝐚}{m_a}}{\displaystyle \frac{e_a𝐤_𝐚^{}}{m_a}})\}`$ (C10)
$`\times f_b\left\{f_a^{}f_a\right\}.`$ (C11)
(C12)
We assume parabolic bands $`ϵ=k^2/2m`$.

The relaxation function $`\delta E/E`$ would correspond to linearization of the $`cos`$ function in (C12) with respect to the field while the relaxation time is obtained taking into account the linearization with respect to the momentum $`p_a`$ of the displaced distributions (3). Cross terms like $`p_aE`$ are already of second order response. The result can be written in the concise form (10).

#### a Relaxation time by neutral impurity scattering

In the following we give an explicit calculation. Employing the Yukawa or Debye potential (C7) one obtains for the relaxation part

$`I_{ab}^R(k_a)=p_a{\displaystyle \frac{f_0}{_{k_a}}}{\displaystyle \frac{2\pi m_a}{\mathrm{}}}g_{ab}^2{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑\alpha {\displaystyle \frac{\mathrm{cos}(\alpha \varphi )\mathrm{cos}\varphi }{(2k_a|\mathrm{sin}\frac{\alpha }{2}|+\mathrm{}\kappa )^2}}`$ (C13)
with the angle between $`k_a`$ and the field direction $`p_a`$ denoted by $`\varphi `$.

The current relaxation time is now obtained by

$`n_a𝐩_𝐚\tau _{ei}^1={\displaystyle \frac{dk_a}{(2\pi \mathrm{})^2}𝐤_𝐚I_{ab}(k_a)}`$ (C15)
from which one gets \[$`\kappa _p=\mathrm{}/2r_0p`$\]

$`\tau _i^1`$ $`=`$ $`{\displaystyle \frac{m_ag_{ab}^2}{2^{3/2}\mathrm{}^3}}{\displaystyle \frac{n_bs_b}{n_a}}{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑p_pf_0\left[{\displaystyle \frac{1}{\kappa _p^21}}+{\displaystyle \frac{\mathrm{ln}\left(\frac{1+\sqrt{1\kappa _p^2}}{\kappa _p}\right)}{(\kappa _p^21)^{3/2}}}\right].`$ (C16)
This current relaxation time in the low temperature Sommerfeld-expansion leads to \[$`\kappa _i=\mathrm{}/2r_0p_{fa}`$\]

$`\tau _i^1`$ $`=`$ $`{\displaystyle \frac{m_ag_{ab}^2}{2^{3/2}\mathrm{}^3}}{\displaystyle \frac{n_bs_b}{n_a}}({\displaystyle \frac{1}{\kappa _i^21}}+{\displaystyle \frac{\mathrm{ln}\left(\frac{1+\sqrt{1\kappa _i^2}}{\kappa _i}\right)}{(\kappa _i^21)^{3/2}}}`$ (C19)
$`+{\displaystyle \frac{\pi ^2}{24}}{\displaystyle \frac{T^2}{ϵ_f^2}}_{\kappa _i}^2[{\displaystyle \frac{1}{\kappa _i^21}}+\kappa _i^4{\displaystyle \frac{\mathrm{ln}\left(\frac{1+\sqrt{1\kappa _i^2}}{\kappa _i}\right)}{(\kappa _i^21)^{3/2}}}]).`$
The second temperature correction is negative and diminishes the positive first part. As long as $`T<ϵ_f`$ the net relaxation time is positive and continously falling to zero for $`\kappa _i\mathrm{}`$.

The high density expansion reads

$`R_i=\tau _i^1`$ $`{\displaystyle \frac{m_a}{n_ae_a^2}}{\displaystyle \frac{e_a^2}{h}}={\displaystyle \frac{2^{3/2}s_bn_b}{s_an_a}}\left({\displaystyle \frac{m_ag_{ab}r_0}{\mathrm{}^2}}\right)^2\kappa _i^2(1+\sqrt{\xi })^2`$ (C23)
$`\times \{1\mathrm{ln}{\displaystyle \frac{\kappa _i}{2}}(5+6\mathrm{ln}{\displaystyle \frac{\kappa _i}{2}}){\displaystyle \frac{\kappa _i^2}{4}}`$
$`{\displaystyle \frac{\pi ^2}{24}}{\displaystyle \frac{T^2}{e_f^2}}(2+(19+12\mathrm{ln}{\displaystyle \frac{\kappa _i}{2}})\kappa _i^2)+o(\kappa _i^3)\}`$
and the low density expansion or short range expansion

$`R_i`$ $`=`$ $`{\displaystyle \frac{2^{3/2}s_bn_b}{s_an_a}}\left({\displaystyle \frac{m_ag_{ab}r_0}{\mathrm{}^2}}\right)^2\kappa _i^2(1+\sqrt{\xi })^2`$ (C26)
$`\times \left\{{\displaystyle \frac{1}{\kappa _i^2}}{\displaystyle \frac{\pi }{2\kappa _i^3}}{\displaystyle \frac{\pi ^2}{24}}{\displaystyle \frac{T^2}{ϵ_f^2}}{\displaystyle \frac{\pi ^3}{16\kappa _i^3}}+o(\kappa _i^4)\right\}`$
#### b Relaxation effect by neutral impurity scattering

The relaxation function is now obtained if we linearize (C12) with respect to the external field. We obtain

$`{\displaystyle \frac{dk_a}{(2\pi \mathrm{})^2}𝐤_𝐚I_{ab}^{\delta E}(k_a)}=𝐄{\displaystyle \frac{n_ie}{m\mathrm{}^3}}{\displaystyle \frac{dkdq}{(2\pi \mathrm{})^4}f_0(ϵ_k)V_s^2(q)q^2}`$ (C28)
$`\times \mathrm{cos}^2(q,E){\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑\tau \tau ^2\mathrm{sin}\left({\displaystyle \frac{q^2+2\mathrm{𝐤𝐪}}{2m\mathrm{}}}\tau \right)`$ (C29)
from which one gets

$`{\displaystyle \frac{\delta E}{E}}`$ $`=`$ $`{\displaystyle \frac{n_i}{4\pi \mathrm{}^5mn_a}}{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑qq^3V_s^2(q){\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑\tau \tau ^2I_s`$ (C30)
$`=`$ $`{\displaystyle \frac{n_i}{n_a}}\kappa _a^2\left({\displaystyle \frac{mg_{ab}r_0}{\mathrm{}^2}}\right)^2{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}{\displaystyle \frac{dy}{(y+\kappa _a)^2}}_y^2\sqrt{y^21}\mathrm{\Theta }(y1)`$ (C31)
where we have used (F30) for the last line. Employing the same regularization due to the principal value, (45), we end up with

$`{\displaystyle \frac{\delta E}{E}}`$ $`=`$ $`{\displaystyle \frac{n_i}{n_a}}\left({\displaystyle \frac{mg_{ab}r_0}{\mathrm{}^2}}\right)^2\left\{{\displaystyle \frac{2\kappa _a^2+\kappa _a^4}{(\kappa _a^21)^2}}+{\displaystyle \frac{3\kappa _a^3\mathrm{ln}(\kappa _a\sqrt{\kappa _a^21})}{(\kappa _a^21)^{5/2}}}\right\}.`$ (C33)
The $`T^2`$ dependent term could be given analogously. The needed low density or short range expansion reads now

$`{\displaystyle \frac{\delta E_i}{E}}`$ $`=`$ $`{\displaystyle \frac{n_i}{n_a}}\left({\displaystyle \frac{mg_{ab}r_0}{\mathrm{}^2}}\right)^2\left\{1+{\displaystyle \frac{43\mathrm{ln}2\kappa _a}{\kappa _a^2}}\right\}+o(\kappa ^4).`$ (C35)
## D Polarization function in 2D

Here we discuss the properties of low temperature polarization function

$`\mathrm{\Pi }(\omega ,q)`$ $`=`$ $`{\displaystyle \frac{dp}{(2\pi \mathrm{})^2}\frac{f_0(\frac{(p+\frac{q}{2})^2}{2m})f(\frac{(p\frac{q}{2})^2}{2m})}{\frac{pq}{m}\omega i0}}.`$ (D1)
The imaginary part is easily rewritten as

$`\mathrm{Im}\mathrm{\Pi }(\omega ,q)=\pi {\displaystyle \underset{0}{\overset{\mathrm{}}{}}}{\displaystyle \frac{dpp}{(2\pi \mathrm{})^2}}f_0({\displaystyle \frac{p^2}{2m}}){\displaystyle \underset{0}{\overset{2\pi }{}}}𝑑\varphi `$ (D3)
$`\times \left\{\delta ({\displaystyle \frac{p.q}{m}}{\displaystyle \frac{q^2}{2m}}\omega )\delta ({\displaystyle \frac{p.q}{m}}+{\displaystyle \frac{q^2}{2m}}\omega )\right\}`$
$`=`$ $`{\displaystyle \frac{m^{3/2}}{2^{3/2}\pi \mathrm{}^2q}}{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}{\displaystyle \frac{dϵ}{\sqrt{ϵ}}}(f_0(ϵ+{\displaystyle \frac{(q/2+m\omega \mathrm{}/q)^2}{2m}})`$ (D5)
$`f_0(ϵ+{\displaystyle \frac{(q/2m\omega \mathrm{}/q)^2}{2m}})).`$
The energy shifts in the distribution function we absorb into an effective chemical potential which should be positive in order to obtain nonzero contribution at Sommerfeld expansion

$`\mu _{\mathrm{eff}}=ϵ_f{\displaystyle \frac{\left(\pm \frac{q}{2}+\frac{m\omega \mathrm{}}{q}\right)^2}{2m}}0`$ (D7)
The low temperature Sommerfeld expansion reads than $`f_0(ϵ)=n((ϵ\mu _{\mathrm{eff}})/T)`$

$`{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}{\displaystyle \frac{dϵ}{\sqrt{ϵ}}}n({\displaystyle \frac{ϵ\mu _{\mathrm{eff}}}{T}})=2{\displaystyle \underset{\mu _{\mathrm{eff}}/T}{\overset{\mathrm{}}{}}}𝑑xn(x)_x\sqrt{Tx+\mu _{\mathrm{eff}}}`$ (D8)
$`=2{\displaystyle \underset{\mu _{\mathrm{eff}}/T}{\overset{\mathrm{}}{}}}𝑑xn(x)(1n(x))\sqrt{Tx+\mu _{\mathrm{eff}}}`$ (D9)
$`=2\sqrt{\mu _{\mathrm{eff}}}\left(1{\displaystyle \frac{\pi ^2T^2}{24\mu _{\mathrm{eff}}}}\right).`$ (D10)
$`=2\left(1{\displaystyle \frac{\pi ^2T^2}{12}}{\displaystyle \frac{}{ϵ_f}}\right)\sqrt{\mu _{\mathrm{eff}}}.`$ (D11)
Therefore it is enough to know the zero temperature result since the $`T^2`$ correction are given simply by derivatives with respect to $`ϵ_f`$.

Introducing dimensionless coordinates as in

$`x={\displaystyle \frac{q}{2p_f}}x_0={\displaystyle \frac{\mathrm{}\omega }{4ϵ_f}}`$ (D12)
we get finally for the imaginary part of the polarization function

$`\mathrm{Im}\mathrm{\Pi }(\omega ,q)={\displaystyle \frac{m}{4\pi \mathrm{}^2x}}`$ (D13)
$`\times \{\mathrm{\Theta }(x|x_0+x^2|)\sqrt{1\left(x+{\displaystyle \frac{x_0}{x}}\right)^2}`$ (D14)
$`\mathrm{\Theta }(x|x_0x^2|)\sqrt{1\left(x{\displaystyle \frac{x_0}{x}}\right)^2}\}`$ (D15)
which is of course the result given in . The corresponding real part is given by the Hilbert transform according to (D1)

$`\mathrm{Re}\mathrm{\Pi }(\omega ,q)=2{\displaystyle \frac{d\omega ^{}}{2\pi }\frac{\mathrm{Im}\mathrm{\Pi }(\omega ^{},q)}{\omega \omega ^{}}}.`$ (D16)
Using the integral

$`f(a)={\displaystyle \underset{1}{\overset{1}{}}}{\displaystyle \frac{\sqrt{1z^2}}{az}}=\pi \{\begin{array}{cc}a\hfill & 1|a|\hfill \\ a\mathrm{sgn}(a)\sqrt{a^21}\hfill & \end{array}`$ (D19)
we obtain

$`\mathrm{Re}\mathrm{\Pi }={\displaystyle \frac{m}{4\pi ^2\mathrm{}^2x}}\left\{f({\displaystyle \frac{x_0}{x}}+x)f({\displaystyle \frac{x_0}{x}}x)\right\}.`$ (D21)
The real and imaginary part is plotted in figure 9.

## E Integrals over dielectric functions

In order to perform the frequency integration in (11) we use a very useful relation, which has been given in

$`{\displaystyle \frac{d\omega }{2\pi }\frac{H(\omega )}{\omega }\mathrm{Im}^1(q,\omega )}={\displaystyle \frac{H(0)}{2}}\mathrm{Re}(1{\displaystyle \frac{1}{(q,0)}}).`$ (E1)
For the integration of (11) we set $`H(\omega )=\mathrm{cos}(\omega \tau +A)\mathrm{cos}(\omega \tau ^{}+B)\omega /\mathrm{Im}`$ with $`A`$ and $`B`$ are the remaining content of the cosine functions of (15) and (16).

Lets first prove the relation (E1). We consider the following integral including the dielectric function

$`I`$ $`=`$ $`{\displaystyle \frac{d\omega }{2\pi }\frac{H(\omega )}{\omega }\mathrm{Im}^1(\omega )}`$ (E3)
$`=`$ $`{\displaystyle \frac{d\omega }{4\pi i}(\frac{1}{\omega +i\eta }+\frac{1}{\omega i\eta })H(\omega )(f^{}f^+)}`$ (E4)
where $`f^+=11/`$ and $`f^{}=(f^+)^{}`$. In the following we will assume that the function $`H(\omega )`$ is analytical. Since $`f^\pm (\omega )`$ has no poles in the lower/upper half plane and vanishes with $`\omega ^2`$ for large $`\omega `$ we have the identity

$`{\displaystyle \frac{d\omega }{2\pi i}H(\omega )\frac{f^\pm (\omega )}{(\omega \pm i\eta )}}=f^\pm (0)H(0)`$ (E5)
and all other combinations of signs vanish. With the help of the relation (E5) we compute easily for (E3)

$`I={\displaystyle \frac{1}{2}}H(0)\mathrm{Re}\left(1{\displaystyle \frac{1}{(0)}}\right)`$ (E6)
which proves relation (E1).

### 1 Regularization of integration

We are now going to give explicit forms including the dielectric function $`=1V(q)\mathrm{\Pi }(q,\omega )`$ where the polarization function $`\mathrm{\Pi }`$ was discussed in the foregoing chapter. The forms appearing throughout the paper are

$`I`$ $`=`$ $`{\displaystyle \frac{d\omega }{2\pi }\frac{h(\omega )}{|(\omega )|^2}}`$ (E7)
$`=`$ $`{\displaystyle \frac{d\omega }{2\pi }\frac{\omega h(\omega )/\mathrm{Im}(\omega )}{\omega }\mathrm{Im}^1(\omega )}`$ (E8)
such that we can apply (E6) with $`H(\omega )=\omega h(\omega )/\mathrm{Im}(\omega )`$. In the case where $`\mathrm{Im}=0`$ appears an ambiguity which we have to remove. We add to the particle-hole fluctuation which forms the polarization an infinitesimal small classical process

$`\delta \mathrm{Im}\mathrm{\Pi }=\eta \omega \mathrm{e}^{c\omega ^2}\eta (\omega +o(\omega ^3)).`$ (E9)
This will make the imaginary part of the polarization nonzero everywhere and will not introduce additional poles in the upper half plane. Therefore we can apply the integration (E6). The corresponding real part according to (E6) will be $`\eta `$ and drop out in the final form (E6).

### 2 Specific forms

Now we write down the required forms for (E6). One gets the static result from (D15) and (D21) at low temperatures

$`\mathrm{\Pi }(0,q)={\displaystyle \frac{}{\mu }}n\{\begin{array}{cc}1\hfill & q<2p_f\hfill \\ 1\sqrt{1\left(\frac{2p_f}{q}\right)^2}\hfill & q>2p_f\hfill \end{array}`$ (E12)
(E13)
with the chemical potential $`\mu `$ and from (LABEL:imp)

$`\mathrm{Im}\mathrm{\Pi }(\omega ,q)=`$ (E14)
$`{\displaystyle \frac{m^2\omega \mathrm{}\mathrm{\Theta }(2p_fq)}{\pi \mathrm{}^2q\sqrt{4p_f^2q^2}}}\left(1+{\displaystyle \frac{8\pi ^2T^2m^2}{(4p_f^2q^2)^2}}\right)`$ (E15)
$`+o(\omega ^2,T^4)`$ (E16)
(E17)
The region where $`\mathrm{Im}\mathrm{\Pi }0`$ correspond exactly to the upper case of (E13). Using this expansion we obtain

$`H(0)=\underset{\omega 0}{lim}{\displaystyle \frac{\mathrm{}\omega }{\mathrm{Im}^{}}}={\displaystyle \frac{\mathrm{}q^2}{\underset{b}{}\frac{m_b^2e_b^2}{\sqrt{4p_{fb}^2q^2}}(1+\frac{8\pi ^2m_b^2T_b^2}{(4p_{fb}^2q^2)^2})}}`$ (E18)
where we have to keep in mind that the above procedure in calculating the frequency integral works only for finite $`\mathrm{Im}\mathrm{\Pi }`$ or finite particle-hole fluctuations. According to (LABEL:imp) this restricts the later $`q`$-integration to values smaller than $`2p_{fb}`$ respectively.

We get finally for (E1)

$`W(q)`$ $`=`$ $`V(q)^2{\displaystyle \frac{1}{2}}\underset{\omega 0}{lim}{\displaystyle \frac{\mathrm{}\omega }{\mathrm{Im}^{}}}\mathrm{Re}(1{\displaystyle \frac{1}{^R(0,q)}})`$ (E20)
$`=`$ $`{\displaystyle \frac{2\pi e_a^2e_b^2\mathrm{}^4\kappa (q)}{q+\mathrm{}\kappa (q)}}{\displaystyle \frac{1}{\underset{b}{}\frac{m_b^2e_b^2}{\sqrt{4p_{fb}^2q^2}}(1+\frac{8\pi ^2m_b^2T_b^2}{(4p_{fb}^2q^2)^2})}}`$ (E21)
where the screening length is from (E13)

$`\kappa `$ $`=`$ $`{\displaystyle \underset{b}{}}2\pi e_b^2_\mu n_b\{\begin{array}{cc}1\hfill & q<2p_{fb}\hfill \\ 1\sqrt{1\left(\frac{2p_{fb}}{q}\right)^2}\hfill & q>2p_{fb}\hfill \end{array}`$ (E25)
and since $`n=\frac{s}{4\pi \mathrm{}^2}p_f^2+o(\mathrm{e}^{ϵ_f/T})`$ one has $`_\mu n=\frac{m_bs_b}{2\pi \mathrm{}^2}`$.

## F Low temperature expansion of Integrals

The integrals occurring in (LABEL:relaxf), (LABEL:rf) and (30) will now be calculated. Using $`\underset{0}{\overset{\mathrm{}}{}}𝑑\tau \mathrm{cos}x\tau =\pi \delta (x)`$ we can write for (B6) and (LABEL:po)

$`{\displaystyle \frac{1}{2}}\mathrm{\Pi }^<(q,\omega =0)={\displaystyle \frac{dp}{(2\pi \mathrm{})^2}f_b(p)(1f_b(p+q))}`$ (F1)
$`\times {\displaystyle \underset{0}{\overset{\mathrm{}}{}}}d\tau ^{}\mathrm{cos}(ϵ_{p+q}ϵ_p){\displaystyle \frac{\tau ^{}}{\mathrm{}}}`$ (F2)
$`={\displaystyle \frac{dp}{(2\pi \mathrm{})^2}f_b(p)(1f_b(p))\pi \mathrm{}\delta \left(ϵ_{p+q}ϵ_p\right)}`$ (F3)
$`={\displaystyle \frac{m}{4\pi \mathrm{}q}}{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑pf_b(p)(1f_b(p)){\displaystyle \underset{1}{\overset{1}{}}}{\displaystyle \frac{dx}{\sqrt{1x^2}}}`$ (F4)
$`\times \left(\delta (x+{\displaystyle \frac{q}{2p}})+\delta (x{\displaystyle \frac{q}{2p}})\right)`$ (F5)
$`={\displaystyle \frac{m_b^2T_b}{\pi \mathrm{}q}}{\displaystyle \underset{\frac{q^2}{8m_bT_b}\frac{ϵ_{fb}}{T_b}}{\overset{\mathrm{}}{}}}𝑑x{\displaystyle \frac{n(x)(1n(x))}{\sqrt{8m_b(T_bx+ϵ_{fb})q^2}}}`$ (F6)
where we used $`x=p^2/2m_bT_bϵ_{fb}/T_b`$ and $`n(x)=1/(\mathrm{e}^x+1)`$ and $`ϵ_{fb}`$ is the Fermi energy. The last integral is only non-zero for negative lower integration limits implying $`2p_{fb}>q`$. Expanding the square root in terms of the temperature $`T_b`$ we obtain finally

$`{\displaystyle \frac{1}{2}}\mathrm{\Pi }^<(q,\omega =0)={\displaystyle \frac{1}{2}}\mathrm{\Pi }^>(q,\omega =0)=`$ (F7)
$`{\displaystyle \frac{m_b^2T_b\mathrm{\Theta }(2p_{fb}q)}{\pi \mathrm{}q\sqrt{4p_{fb}^2q^2}}}\left(1+{\displaystyle \frac{8\pi ^2m_b^2T_b^2}{(4p_{fb}^2q^2)^2}}\right)`$ (F8)
(F9)
The integrals (LABEL:relaxf), (LABEL:rf) can be tremendously simplified observing that (30) can be written

$`I_s(a,\tau )={\displaystyle 𝑑kf_k(1f_{kq})\mathrm{sin}\left(ϵ_{kq}ϵ_k\right)\frac{\tau }{\mathrm{}}}`$ (F10)
$`=`$ $`{\displaystyle 𝑑k(f_{kq}f_k)g_{ϵ_{kq}ϵ_k}\mathrm{sin}\left(ϵ_{kq}ϵ_k\right)\frac{\tau }{\mathrm{}}}`$ (F11)
$`=`$ $`{\displaystyle }dkf_k(g_{ϵ_{k+q}ϵ_k}\mathrm{sin}(ϵ_kϵ_{k+q}){\displaystyle \frac{\tau }{\mathrm{}}}`$ (F13)
$`g_{ϵ_kϵ_{kq}}\mathrm{sin}(ϵ_{kq}ϵ_k){\displaystyle \frac{\tau }{\mathrm{}}})`$
$`=`$ $`{\displaystyle 𝑑kf_k\mathrm{sin}\left(ϵ_kϵ_{kq}\right)\frac{\tau }{\mathrm{}}\left(g_{ϵ_{kq}ϵ_k}+g_{ϵ_kϵ_{kq}}\right)}`$ (F14)
$`=`$ $`{\displaystyle 𝑑kf_k\mathrm{sin}\left(ϵ_{kq}ϵ_k\right)\frac{\tau }{\mathrm{}}}`$ (F15)
where $`g_x=1/(\mathrm{e}^{x/T}1)`$ and we have used $`kk`$ transformation in coming from the third to the fourth equality.

The time integral (LABEL:rf) can be now represented as a derivative of a $`\delta `$ function with respect to $`k`$. A partial integration leads than to

$`{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑\tau \tau I_s(a,\tau )={\displaystyle \frac{dk}{(2\pi \mathrm{})^2}f_k\underset{0}{\overset{\mathrm{}}{}}𝑑\tau \tau \mathrm{sin}\left(ϵ_{kq}ϵ_k\right)\frac{\tau }{\mathrm{}}}`$ (F16)
$`={\displaystyle \frac{m_a^2}{4\pi q^2}}{\displaystyle \underset{q/2}{\overset{\mathrm{}}{}}}{\displaystyle \frac{dk}{k}}_k(kf_a(k)){\displaystyle \underset{1}{\overset{1}{}}}{\displaystyle \frac{dx}{x\sqrt{1x^2}}}`$ (F17)
$`\times \left(\delta (x{\displaystyle \frac{q}{2p}})\delta (x+{\displaystyle \frac{q}{2p}})\right)`$ (F18)
$`={\displaystyle \frac{m_a^2}{\pi q^3}}{\displaystyle \underset{q/2}{\overset{\mathrm{}}{}}}𝑑k_k(kf_a(k)){\displaystyle \frac{k}{\sqrt{k^2\frac{q^2}{4}}}}.`$ (F19)
$`={\displaystyle \frac{m_a^{3/2}}{4\sqrt{2}\pi q}}{\displaystyle \underset{a/T_a}{\overset{\mathrm{}}{}}}𝑑xn(x)(1n(x)){\displaystyle \frac{\mathrm{\Theta }(2p_{fa}q)}{\sqrt{T_ax+a}}}`$ (F20)
with $`a=ϵ_{fa}q^2/8m_a`$. Expanding the argument in terms of $`T_a`$ one arrives analogously to (F9) at the result

$`{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑\tau \tau I_s(a,\tau )={\displaystyle \frac{m_a^2}{4\pi q\sqrt{4p_{fa}^2q^2}}}\left(1+{\displaystyle \frac{8\pi ^2m_a^2T_a^2}{(4p_{fa}^2q^2)^2}}\right)`$ (F21)
$`\times \mathrm{\Theta }(2p_{fa}q).`$ (F22)
The integral (LABEL:relaxf) requires some more care. We use the principal value identity $`\underset{0}{\overset{\mathrm{}}{}}𝑑\tau \mathrm{sin}\tau x=𝒫/x`$ and write

$`{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑\tau \tau ^2I_s(a,\tau )=`$ (F23)
$`{\displaystyle \frac{m_a^3\mathrm{}}{\pi ^2q^3}}𝒫{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑kf_a(k)_q^2{\displaystyle \underset{0}{\overset{2\pi }{}}}{\displaystyle \frac{d\varphi }{\frac{q}{2k}\mathrm{cos}\varphi }}.`$ (F24)
Using

$`{\displaystyle \underset{0}{\overset{2\pi }{}}}{\displaystyle \frac{d\varphi }{a\mathrm{cos}\varphi }}={\displaystyle \frac{2\pi }{\sqrt{a^21}}}\mathrm{\Theta }(a1)`$ (F25)
we can write after one partial integration

$`{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑\tau \tau ^2I_s(a,\tau )=`$ (F26)
$`{\displaystyle \frac{m_a^3\mathrm{}𝒫}{\pi q^3}}_q^2{\displaystyle \underset{ϵ_{fa}/T}{\overset{q^2/8m_aT_aϵ_{fa}/T_a}{}}}𝑑xn(x)(1n(x))`$ (F27)
$`\times \sqrt{q^28m_aT_ax4p_{fa}^2}.`$ (F28)
Expanding again the argument in terms of $`T_a`$ we arrive at

$`{\displaystyle \underset{0}{\overset{\mathrm{}}{}}}𝑑\tau \tau ^2I_s(a,\tau )={\displaystyle \frac{m_a^3\mathrm{}𝒫}{\pi q^3}}`$ (F29)
$`\times {\displaystyle \frac{^2}{q^2}}\left(\sqrt{q^24p_{fa}^2}\left(1{\displaystyle \frac{8\pi ^2m_a^2T_a^2}{3(q^2p_{fa}^2)^2}}\right)\mathrm{\Theta }(q2p_{fa})\right).`$ (F30)


format: text

text:
# Evidence for 𝑀_𝐵 and 𝑀_𝐶 phases in the morphotropic phase boundary region of (1-𝑥)[𝑃𝑏(𝑀𝑔_{1/3}𝑁𝑏_{2/3})𝑂₃]-𝑥𝑃𝑏𝑇𝑖𝑂₃ : A Rietveld study

## 1 Introduction

Relaxor ferroelectric based morphotropic phase boundary (MPB) ceramics like $`(1x)[Pb(Mg_{1/3}Nb_{2/3})O_3]xPbTiO_3(PMNxPT)`$  and $`(1x)[Pb(Zn_{1/3}Nb_{2/3})O_3]xPbTiO_3(PZNxPT)`$  show much higher electromechanical response about their MPBs in comparison to the well known $`Pb(Zr_xTi_{1x})O_3`$ (PZT) system . The reason why relaxor based MPB systems have much higher electromechanical response is still not very clear eventhough recent theoretical and experimental developments in PZT have improved our understanding of the phase stabilities in the vicinity of the MPB . Noheda et al have discovered that the tetragonal phase of PZT with compositions ($`x=0.50,0.52`$) close to the MPB transforms to a monoclinic phase with space group Cm at low temperatures . Ragini et al  and Ranjan et al  have discovered yet another low temperature phase transition in which the Cm monoclinic phase transforms to another monoclinic phase with Cc space group . The Cm to Cc phase transition is an antiferrodistortive (AFD) transition leading to superlattice reflections which are observable in the electron  and neutron  diffraction patterns only and not in the XRD patterns as a result of which Noheda et al missed the Cc phase in their high resolution XRD studies at low temperatures. The tetragonal to Cm, and Cm to Cc transitions are accompanied with pronounced anomalies in the elastic constant and dielectric constant . It has been argued  that the monoclinic Cm phase provides the path for polarization rotation between tetragonal (P4mm) and rhombohedral (R3m) phases. X-ray Rietveld analysis by Ragini et al , has, however, revealed that the hitherto believed rhombohedral phase of PZT for $`0.53<x<0.62`$  is indeed monoclinic (Cm) with very small domain size leading to composition dependent anomalous broadening of various reflections. Thus the MPB in the PZT system separates the stability fields of tetragonal and monoclinic Cm phases . On application of DC field, these monoclinic domains get aligned and merged as a result of which some of the XRD peaks showing anomalous broadening in the unpoled state start exhibiting splittings characteristic of the Cm phase in the poled state. Thus, according to Ragini et al , the field induced rhombohedral to Cm transition reported by Guo et al  is really a transition from a small-domain Cm phase to large-domain Cm phase. Based on Rietveld analysis of the XRD data, Ragini et al  have also shown that the tetragonal and monoclinic (Cm) phases coexist across the MPB in the composition range $`0.520x0.525`$ due to nucleation barrier to the first order transition between the high temperature tetragonal and the low temperature monoclinic Cm phases .

These recent developments in PZT have been followed up by similar studies on the structure of MPB phases in the PMN-$`x`$PT  and PZN-$`x`$PT  systems. In these systems also, the structure of the morphotropic phase in the unpoled state is monoclinic but with a space group Pm , which is different from that in the PZT system. The Pm space group proposed by Singh and Pandey  and Kiat et al  in the MPB region of the PMN-xPT system has recently been confirmed in the high resolution powder XRD studies by Noheda et al  contradicting an earlier report of Cm space group by the same workers for a similar composition . However in the PZN-$`x`$PT system, the possibility of monoclinic Pm  or orthorhombic Bmm2  structures in the MPB region continues to be debated. More interestingly, Noheda et al  and Ohwada, et al  have observed a field-induced irreversible rhombohedral to Pm monoclinic phase transition in PZN-0.8PT through the Cm monoclinic phase.

Using eighth-order expansion of Devonshire theory, Vanderbilt and Cohen  have predicted different regions of stability for the monoclinic Pm and Cm phases that are designated as $`M_C`$ and $`M_A/M_B`$, respectively, in their paper. Although both $`M_A`$ and $`M_B`$ phases belong to the Cm space group, the difference lies in the magnitudes of the components of the polarization ($`P`$) corresponding to the pseudocubic cell. For the $`M_A`$ phase $`P_X=P_YP_Z`$ with $`P_Z>P_X`$, while for the $`M_B`$ phase, $`P_X=P_YP_Z`$ with $`P_Z<Px`$. As per the phase diagram of Vanderbilt and Cohen , one expects a narrow stability field of the $`M_B`$ phase between the rhombohedral and $`M_C`$ phases. The present work was undertaken to verify the existence of the Cm ($`M_B`$) phase for compositions in between those for the rhombohedral and monoclinic (Pm) phases using Rietveld analysis of X-ray powder diffraction data on PMN-$`x`$PT samples with $`x`$ varying from 0.26 to 0.39 at an interval of $`\mathrm{\Delta }x`$ = 0.01. From a careful study of the variation of the dielectric constant and crystal structure with composition ($`x`$) on unpoled PMN-$`x`$PT ceramics, we show that the dominant phases in the composition ranges $`0x`$ 0.26, $`0.27x0.30`$, $`0.31x0.34`$ and $`0.35x1`$ are rhombohedral (R3m), monoclinic $`M_B`$ (Cm), monoclinic $`M_C`$ (Pm) and tetragonal (P4mm), respectively, in reasonable agreement with the predictions of the Vanderbilt and Cohen’s theory .

## 2 Experimental

Samples used in the present work were prepared by a modified solid state route . One of the common problems associated with the solid state synthesis of PMN-$`x`$PT ceramics is the appearance of an unwanted pyrochlore phase . To get rid of this unwanted phase, off-stoichiometric compositions, with excess of MgO and PbO, are used . For example, Noheda et al  have used 15.5 and 2wt$`\%`$ excess of MgO and PbO for getting pure perovskite phase. This naturally perturbs the phase stabilities in the vicinity of the MPB where the crystal structure is very sensitive to even small variations in the composition because of nearly degenerate nature of various phases. In order to bring out the intrinsic features of the PMN-$`x`$PT system, it is imperative to prepare pyrochlore phase free PMN-$`x`$PT ceramics in stoichiometric compositions (i.e., without using any excess of PbO and MgO). We have achieved this by using $`PbCO_3`$ and $`MgCO_3.3H_2O`$, instead of PbO and MgO, respectively, and introducing one more step in the reaction sequence for mixing of $`TiO_2`$ . In the present work, AR grade $`Nb_2O_5`$ (99.95 % ) , $`TiO_2`$ (99 %), $`Mg(NO_3)_2.6H_2O`$ (99%), $`Pb(NO_3)_2`$ (99 %) and ammonium carbonate were used. $`MgCO_3.3H_2O`$ and $`PbCO_3`$ were prepared from $`Mg(NO_3)_2.6H_2O`$ and $`Pb(NO_3)_2`$ by precipitation. Mixing of various ingredients in stoichiometric proportions was carried out for 6 hours using a ball mill (Retsch, Japan) with zirconia jars and zirconia balls. AR grade acetone was used as the mixing media. Heat treatments for calcination were carried out in alumina crucibles using a globar furnace. The columbite precursor $`MgNb_2O_6`$ (MN)  was prepared by calcining a stoichiometric mixture of $`MgCO_3.3H_2O`$ and $`Nb_2O_5`$ at $`1050^oC`$ for six hours. At the next stage, stoichiometric amount of $`TiO_2`$ was mixed with $`MgNb_2O_6`$ and the mixture was calcined at $`1050^oC`$ for six hours to obtain $`[(1x)/3]MgNb_2O_6(x)TiO_2`$ (MNT) precursor. This MNT precursor was then mixed with stoichiometric amount of $`PbCO_3`$ and calcined at $`750^oC`$ for six hours. The powder obtained at this stage consists of pure perovskite phase of PMN-$`x`$PT free from the pyrochlore phase. Cold compaction of calcined powders was done using a steel die of 12-mm diameter and an uniaxial hydraulic press at an optimised load of 65 kN. 2 % polyvinyl alcohol (PVA) solution in water was used as binder. The green pellets were kept at $`500^oC`$ for 10 hours to burn off the binder material and then sintered at $`1150^oC`$ for 6 hours in sealed crucibles with controlled PbO atmosphere. Density of the sintered pellets was higher than 98% of the theoretical density. Sintered pellets were crushed into fine powders and then annealed at $`500^oC`$ for 10 hours to remove the strains introduced during crushing for x-ray characterizations. XRD measurements were carried out using a 12kW rotating anode (Cu) based Rigaku powder diffractometer operating in the Bragg-Brentano geometry and fitted with a graphite monochromator in the diffracted beam. Fired-on silver paste was used for electroding the sintered pellets. The dielectric measurements at 1kHz were carried out using a HIOKI 3532 LCR HiTester.

## 3 Details of the Rietveld refinement

Rietveld refinement was carried out using DBWS-9411 programme . In all the refinements pseudo-Voigt function was used to define the peak profiles while a fifth order polynomial was used for describing the background. Except for the occupancy parameters of the ions, which were kept fixed at the nominal composition, all other parameters i.e., scale factor, zero correction, background, half width parameters along with mixing parameters, lattice parameters, positional coordinates and isotropic thermal parameters were refined. The isotropic thermal parameter values for Pb was invariably found to be high as reported by Kiat et al also . Use of anisotropic thermal parameters for Pb did not lead to any improvement in the agreement factors.

In the tetragonal phase with P4mm space group, the $`Pb^{2+}`$ ion occupies 1(a) sites at $`(0,0,z)`$, $`Ti^{4+}/Nb^{5+}/Mg^{2+}`$ and $`O_I^2`$ occupy 1(b) sites at $`(1/2,1/2,z)`$ and $`O_{II}^2`$ occupy 2(c) sites at $`(1/2,0,z)`$. For the rhombohedral phase with R3mH space group, we used hexagonal axes with lattice parameters $`a_H=b_H=\sqrt{2}a_R`$ and $`c_H=\sqrt{3}a_R`$ where $`a_R`$ corresponds to the rhombohedral cell parameter. In the asymmetric unit of the structure of the rhombohedral phase with R3mH space group, $`Pb^{2+}`$ and $`Nb^{5+}/Ti^{4+}/Mg^{2+}`$ ions occupy 3(a) sites at $`(0,0,z)`$ and $`O^2`$ at the 9(b) site at $`(x,2x,z)`$. In the monoclinic phase with space group Cm, there are four ions in the asymmetric unit with $`Pb^{2+},Ti^{4+}/Nb^{5+}/Mg^{2+}`$ and $`O_I^2`$ in 2(a) sites at $`(x,0,z)`$ and $`O_{II}^2`$ in 4(b) sites at $`(x,y,z)`$. The asymmetric unit of the monoclinic phase with space group Pm has got five ions with $`Pb^{2+}`$ and $`O_I^2`$ in 1(a) site at $`(x,0,z)`$, $`Ti^{4+}/Nb^{5+}/Mg^{2+},O_{II}^2`$ and $`O_{III}^2`$ in 1(b) sites at $`(x,1/2,z)`$. Following the established conventions, $`Pb^{2+}`$ was fixed at (0,0,0) for the tetragonal  and monoclinic structures. Following Megaw and Darlington , the $`z`$coordinate of $`O^2`$ was fixed at 1/6 for the rhombohedral structure. Additionally, space group Bmm2 was also taken into consideration for a few compositions. For this space group, $`Pb^{2+}`$ ion occupies 2(b) sites at $`(1/2,1/2,z),Nb^{5+}/Ti^{4+}/Mg^{2+}`$ ions occupy 2(a) sites at $`(0,0,z),O_I^2`$ in 4(d) sites at $`(x,0,z)`$ and $`O_{II}^2`$ in the 2(b) sites at $`(0,1/2,z)`$. $`Nb^{5+}/Ti^{4+}/Mg^{2+}`$ ions were kept at the origin (0,0,0) for the refinment .

## 4  Location of the morphotropic phase boundary

Lead magnesium niobate (PMN) is a relaxor ferroelectric with very high value of room temperature dielectric constant ($`12000`$ in ceramic form) . With the addition of lead titanate (PT), whose dielectric constant is very low $`(<400)`$, it is expected that the dielectric constant of the resulting solid solution will decrease in comparison to PMN with increasing PT content. Fig.1 shows the variation of room temperature dielectric constant $`ϵ^{}`$ with composition $`(x)`$ for the PMN-$`x`$PT ceramics in the composition range $`0.20x0.45`$. As expected, dielectric constant decreases with increasing value of $`x`$ upto $`x=0.26`$. However, from $`x=0.27`$, the $`ϵ^{}x`$ plot takes an upward trend marking the onset of the MPB region. This upward trend continues upto $`x0.30`$ and thereafter shows a plateau region for $`0.30<x<0.34`$. Kelly et al  have also observed a similar plateau region but in poled PMN-$`x`$PT samples. The dielectric constant again shows an upward trend leading to a peak around $`x=0.35`$ and thereafter it decreases monotonically with increasing $`x`$. The results shown in this figure correspond to averaging over at least 5 samples for each composition. The sample to sample variation of dielectric constant for each composition was less than 1% for various PMN-$`x`$PT samples.

Fig.1 reveals the presence of four different regions. For correlating these regions with a corresponding change in the crystal structure as a function of composition (x), we present in Fig.2 the powder XRD profiles of the 200, 220 and 222 pseudocubic reflections for various PMN-$`x`$PT composition. For the composition range $`0.20x0.26`$, the 200 is a singlet, while 220 and 222 are doublets with weaker reflections occurring on the lower 2$`\theta `$ side. This characterizes a rhombohedral phase that is stable for $`x0.26`$. For $`x>0.26`$, the width of the 200 profile increases eventually leading to an asymmetric tail on the higher 2$`\theta `$ side which has become quite apparent for $`x=0.29`$ and 0.30. As shown in the next section, Rietveld analysis of the XRD data reveals that the structure of the dominant phase in the composition range $`0.26<x<0.31`$ is monoclinic ($`M_B`$ type) with Cm space group. The nature of the 200 profile again changes around $`x=0.31`$ leading to the appearance of a shoulder on the higher 2$`\theta `$ side which eventually becomes a distinct peak with increasing $`x`$ as can be seen from Fig. 2 for $`0.31x0.34`$. In this composition range, the dominant phase is monoclinic ($`M_C`$ type) with Pm space group . For $`x0.35`$, the profiles shown in Fig. 2 exhibit further changes. In particular, 200 pseudocubic reflection splits into 002 and 200/020 with nearly 1:2 intensity ratio. Further, the shoulder/peak on the lower 2$`\theta `$ side of the 220 pseudocubic profile is replaced by a distinct peak on the higher 2$`\theta `$ side. In addition, the 222 profile becomes a singlet. All these features correspond to the tetragonal structure and hence the dominant phase for $`x0.35`$ is tetragonal, as confirmed by the Rietveld analysis also, the results of which are presented in the next section. Thus the different regions shown in Fig. 1 correspond to four different crystallographic phases of PMN-$`x`$PT, which are stable over different range of composition.

## 5 Rietveld analysis of XRD data

### 5.1 Rhombohedral structure with space group R3mH $`(0x0.26)`$

Fig.3 depicts the observed, calculated and difference profiles obtained by Rietveld analysis of the XRD data for PMN-$`x`$PT with $`x=0.20`$ and 0.26 using rhombohedral space group R3mH. The fit between the observed and calculated profiles is quite good confirming the rhombohedral structure of PMN-$`x`$PT for $`x0.26`$ in region I of Fig.1. The refined structural parameters and various agreement factors are given in Table1.

### 5.2  Monoclinic structure with space group Cm $`(0.27x0.30)`$

For compositions with $`x0.27`$, the 200 reflection becomes broader which can not be accounted for in terms of the rhombohedral structure for which 200 is a singlet. This anomalous broadening is similar to that reported in $`Pb(Fe_{1/2}Nb_{2/3})O_3`$  and PZT with $`0.530x0.62`$ , where it has been attributed to the Cm phase. The anomalous broadening is absent for $`x0.26`$ as can be seen from the excellent fit shown in the insets (b) to Fig. 3 for the 200 profile. To determine the true symmetry in the composition range $`0.27x0.30`$, we first carried out Rietveld refinements using various plausible space groups i.e., rhombohedral R3mH, monoclinic Cm, monoclinic Pm and orthorhombic Bmm2. Fig.4 shows the observed, calculated and difference profiles alongwith the various agreement factors for the pseudocubic 200, 220, 310 and 222 reflections using four different space groups for $`x=0.29`$. For the R3mH space group \[Fig. 4(a)\], we see that the mismatch between the observed and calculated profiles is quite prominent for 200 and 310 pseudocubic reflections, which is also confirmed by highest value of the agreement factors. Thus R3mH space group is simply ruled out. For the space group Pm, the misfit between the observed and calculated profiles for the 220 and 222 pseudocubic reflections is very large. In particular, for the 222 pseudocubic profile, the observed and calculated peaks are appearing at different 2$`\theta `$ values ruling out the possibility of the Pm phase. A similar misfit for the 220 and 222 profiles is observed for the Bmm2 space group also as can be seen from Fig. 4(c). The Cm space group gives the most satisfactory fit between the observed and calculated profiles for all the four reflections as can be seen from Fig.4 (d). This is corroborated by the lowest value of the agreement factors also. Fig. 5 depicts the observed, calculated and difference profiles in the 2$`\theta `$ range 20 to 120 degrees for $`x=0.29`$. The overall fit is quite satisfactory. The refined structural parameters are given in Table 2. From an analysis of the refined positional coordinates given in Table 2, it is found that the Cm phase of the PMN-$`x`$PT system is of $`M_B`$ type ($`Px=Py>Pz`$) in contrast to the PZT system where the Cm phase corresponds to the $`M_A`$ type ($`Px=Py<Pz`$) .

### 5.3  Monoclinic structure with space group Pm $`(0.31x0.34)`$

On increasing the PT content beyond $`x`$ = 0.30, new features, like a shoulder in the 200 pseudocubic profile, appear. In order to determine the correct space group of PMN-$`x`$PT in this composition range, we considered Cm, Bmm2, and Pm space groups in our Rietveld analysis. Fig.6. depicts the observed, calculated and difference profiles of PMN-$`x`$PT with $`x`$ = 0.32 for the pseudocubic 200, 220 and 310 reflections for the three space groups. It is evident from this figure that the best fit is obtained for the Pm space group which corresponds to the $`M_C`$ phase in the notation of Vanderbilt and Cohen . The agreement factors given in the last column of Fig. 6 are the lowest for the Pm space group. Fig.7 depicts the observed, calculated and difference profiles in the 2$`\theta `$ range 20 to 120 degrees. The overall fit is quite satisfactory. Table 3 lists the refined structural parameters. It may be noted that the convention used for $`\beta (>90)`$ in Table 2 is different from that $`(<90)`$used in reference  as a result of which the positional coordinates also appear to be different.

### 5.4  Tetragonal structure with space group P4mm $`(0.35x1)`$

Rietveld analysis for $`x0.35`$ confirmed that the dominant phase of PMN-$`x`$PT for these compositions has got tetragonal structure. Very good fit between the observed and calculated profiles were obtained using tetragonal P4mm space group as can be seen from Fig.8 for $`x=0.39`$. The refined structural parameters are listed in Table 4 along with the agreement factors for this composition.

### 5.5 Phase coexistence

One often observes coexistence of neighbouring phases in the MPB region due to extrinsic factors like compositional fluctuations  and intrinsic factors like a first order phase transition between the low and high temperature phases . The results of the previous section show that in the PMN-$`x`$PT system, there are three phase boundaries occurring around $`0.26x0.27`$, $`0.30x0.31`$ and $`0.34x0.35`$ separating the stability fields of rhombohedral and Cm, Cm and Pm, and Pm and tetragonal phases, respectively. In order to see if further improvements in the agreement factors can result from a consideration of the coexistence of a minority neighbouring phase, we carried out Rietveld refinements for the composition ranges $`0.27x0.30`$, $`0.31x0.34`$ and $`0.35x0.39`$ using various plausible coexisting phases. It was found that in the composition range $`0.27x0.30`$, consideration of a minority rhombohedral phase led to higher agreement factors while minority monoclinic Pm phase decreased the agreement factors. The fits between observed and calculated profiles have improved for the (Cm + Pm) model as can be seen from a comparison of Fig. 4 (e) with Fig. 4 (d). Similarly, for the composition range $`0.31x0.34`$, consideration of a minority tetragonal phase decreased the agreement factors whereas the minority Cm phase increased the agreement factors. The presence of minority tetragonal phase improves the fit, especially on the lower 2$`\theta `$ side of the 200 pseudocubic profile, as can be seen from a comparison of Fig.6 (c) with 6(d). Further, monoclinic Pm phase was found to coexist as a minority phase in the tetragonal region $`0.35x0.39`$ in agreement with the results of Ref. . The molar fractions of the minority and majority phases obtained by Rietveld refinement are plotted in Fig.9 as a function of PT content (x). It is evident from this figure that pure R3m phase exists for $`x<0.27`$. For $`x=0.27`$, the structure corresponds to that of pure Cm phase. On increasing the PT content (x), the Cm phase fraction decreases while the fraction of minority Pm phase increases.However, on crossing the Cm-Pm phase boundary at $`0.30<x<0.31`$, the fraction of the Pm phase increases abruptly. For $`x=0.31`$, the structure corresponds to pure Pm phase. On increasing $`x`$ further ($`>0.31`$), the fraction of the majority Pm phase decreases while that of the minority P4mm phase increases with increasing x in the composition range $`0.31<x<0.35`$. For compositions with $`x>0.34`$, the P4mm phase becomes the majority phase whose fraction increases with $`x`$ while the fraction of the minority Pm phase continuously decreases.

### 5.6  Variation of lattice parameters with composition

Variation of lattice parameters with composition (x) for the majority phase is plotted in Fig. 10 for $`0.20x0.45`$. The  and  directions of the tetragonal phase correspond to the  and  directions of the Pm phase respectively. The  direction of the Pm phase deviates slightly from  direction of the tetragonal phase towards the  direction of the Pm phase giving rise to a monoclinic cell with unique b- axis. The  and  directions of the Cm phase, on the otherhand, are along the $`<110>`$ directions of the Pm and tetragonal phases. The cell parameters $`a_m`$, $`b_m`$ of the Cm phase are related to the elementary perovskite cell parameters $`a_p`$, $`b_p`$ as: $`a_pa_m`$/$`\sqrt{2}`$ and $`b_pb_m`$/$`\sqrt{2}`$. For the sake of easy comparison with the corresponding cell parameters of the tetragonal and Pm phases, we have plotted $`a_p`$ and $`b_p`$ instead of $`a_m`$, $`b_m`$ for the Cm phase in Fig.10. In order to maintain the polarization rotation path  in going from tetragonal to Pm to Cm phases for which $`Pz0`$ ($`Px,Py=0`$), $`PzPx0`$ ($`Py=0`$) and $`Px=Py0`$, $`Pz0`$, respectively, the $`a,b,c`$ axes of the Pm phase become $`b_p`$, $`c_m`$, $`a_p`$, respectively, of the Cm phase. It is evident from Fig.10 that for the tetragonal compositions, the $`a`$ parameter increases while the $`c`$ parameter decreases continuously with decreasing x. Around $`0.34<x<0.35`$, the $`a`$ parameter of the tetragonal phase matches with the $`b`$ parameter of the monoclinic (Pm) phase while the $`c`$ parameter of the tetragonal phase, which remains as the $`c`$ parameter of the Pm phase, shows a discontinuous drop. The $`a`$ and $`c`$ parameters of the Pm phase are nearly independent of composition but the b- parameter increases continuously with decreasing $`x`$. Further the monoclinic angle $`\beta `$ decreases continuously with decreasing x in the Pm phase field. The $`b,a`$ and $`c`$ parameters of the Pm phase, which become $`c_m`$, $`b_p`$ and $`a_p`$ of the Cm phase, do not show any discontinuity at the Pm-Cm phase boundary. Similarly, there is no discontinuous change in the $`b_p`$ and $`c_m`$ cell parameters at the Cm-R3m phase boundary but $`a_p`$ drops discontinuously. Table 5 lists the lattice parameter values of the majority phases for all the compositions studied by us.

## 6 Concluding remarks

The phase diagram of Vanderbilt and Cohen  for an eight order expansion of the free energy predicts the stability regions of three types of monoclinic phases, $`M_A`$, $`M_B`$, $`M_C`$, in addition to the tetragonal(T), rhombohedral(R) and orthorhombic(O) phases(see Fig.11). The R-$`M_A`$-T sequence of phase transition observed in PZT as a function of composition has been attributed to the region near $`\alpha =\pi /2`$, $`\beta =0.102`$ by Vanderbilt and Cohen. For the PMN-$`x`$PT system, we have shown that the stable phases in the composition ranges $`x<0.27`$, $`0.26<x<0.31`$, $`0.30<x<0.35`$ and $`x>0.34`$ correspond to R, $`M_B`$, $`M_C`$ and T phases, respectively. In the phase diagram shown in Fig.11, the R- phase region is followed by a narrow stability region of the $`M_B`$ phase in broad agreement with our observations. However, as per this phase diagram, the $`M_B`$ and $`M_C`$ regions should be separated by a very thin orthorhombic (O) phase region. According to our Rietveld analysis results, the $`M_BM_C`$ phase boundary occurs around $`0.30<x<0.31`$. Interestingly, in the Rietveld refinement for $`x=0.30`$, which is near this phase boundary, we found that $`M_B`$, $`M_C`$ and O phases give the same value of $`R_{WP}`$ (12.92) but the $`R_B`$ is the lowest for the O phase ($`R_B`$ = 12.84, 10.04, 9.92 for the $`M_B`$, $`M_C`$ and O phases, respectively) raising the possibility of the existence of the O phase in between the $`M_B`$ and $`M_C`$ phase regions. Thus the phase transition sequence $`RM_BOM_CT`$ predicted by Vanderbilt and Cohen for $`3\pi /4<\beta <0.8\pi `$ may indeed correspond to the PMN-$`x`$PT system. Obviously, the structure of the PMN-$`x`$PT system in the MPB region is much more complex as compared to that in the PZT system with a simple $`RM_AT`$ sequence of phase transitions. Although Vanderbilt and Cohen’s theory predicts that $`RM_B`$ phase boundary to be of first order type, our Rietveld analysis does not reveal any coexistence of R and $`M_B`$ phases. However, since the nature of the XRD profiles for the two phases are quite similar, except for the anomalous broadening of h00 and hh0 reflections for the $`M_B`$ phase, it may never be possible to settle the issue of coexistence of these two phases in a reliable fashion. The coexistence of $`M_C`$ and T phases revealed by our Rietveld analysis is not expected on the basis of the Vanderbilt and Cohen’s theory since the corresponding boundary is of second order type. This could be due to the limitations of the eight order truncation of the free energy expansion.

In the PZN-$`x`$PT system, there is some controversy about the structure of the MPB phase. According to Orauttapong et al , the sequence of phase transition in unpoled samples is R-O-T which is expected for $`\pi <\beta <3\pi /2`$ in the Vanderbilt and Cohen’s phase diagram. Kiat et al have , however, shown that the structure of PZN-$`x`$PT in the MPB region for $`x=0.09`$ corresponds to the $`M_C`$ phase. If it is so, we suspect the existence of $`M_B`$ phase and possibly O phase also interposed between R and $`M_C`$ phases, similar to what we have observed in the present study on the PMN-$`x`$PT system. It is likely that the relaxor ferroelectric based MPB systems may have similar sequence of phase transitions. Further, we suspect that the higher electromechanical response of these relaxor based MPB systems may be linked with the ease of polarization rotation in the presence of $`M_B`$, $`M_C`$ and probably O phases in the morphotropic phase boundary region as compared to the presence of only one phase ($`M_A`$) in the PZT system.

## 7 Acknowledgement

AKS acknowledges the award of senior research fellowship of UGC-BHU.

Figure Captions

Fig.1 Variation of the real part of the dielectric constant ($`ϵ^{}`$) with composition (x) at room temperature for PMN-$`x`$PT ceramics.

Fig.2 Evolution of the X-ray diffraction profiles of the 200, 220 and 222 pseudocubic reflections with composition (x) for PMN-$`x`$PT ceramics.

Fig.3 Observed (dots), calculated (continuous line) and difference (bottom line) profiles obtained after the Rietveld refinement of PMN-$`x`$PT with $`x`$=0.20 and $`x`$=0.26 using rhombohedral space group R3m in the 2$`\theta `$ range 20 to 60 degrees. Inset (a) shows the patterns in the 2$`\theta `$ range 60 to 120 degrees while the inset (b) illustrates the quality of fit for the 200 reflection. Tick marks above the difference profle show peak positions for CuK$`\alpha 1`$.

Fig.4 Observed (dots), calculated (continuous line) and difference (bottom line) profiles of the 200, 220, 310 and 222 pseudocubic reflections obtained after the Rietveld refinement of PMN-$`x`$PT with x=0.29 using different structural models (a) Rhombohedral R3m (b) Monoclinic Pm (c) Orthorhombic Bmm2 (d) Monoclinic Cm and (e) Monoclinic (Pm+Cm) coexistence model.

Fig.5 Observed (dots), calculated (continuous line) and difference (bottom line) profiles obtained after the Rietveld refinement of PMN-$`x`$PT with $`x`$=0.29 using monoclinic space group Cm in the 2$`\theta `$ range 20 to 60 degrees. Inset shows the patterns in the 2$`\theta `$ range 60 to 120 degrees. Tick marks above the difference profle show peak positions for CuK$`\alpha 1`$.

Fig.6 Observed (dots), calculated (continuous line) and difference (bottom line) profiles of the 200, 220, and 310 pseudocubic reflections obtained after the Rietveld refinement of PMN-$`x`$PT with x=0.32 using different structural models (a) Monoclinic Cm (b) Orthorhombic Bmm2 (c) Monoclinic Pm and (e) Monoclinic and tetragonal (Pm+P4mm) coexistence model.

Fig.7 Observed (dots), calculated (continuous line) and difference (bottom line) profiles obtained after the Rietveld refinement of PMN-$`x`$PT with for $`x`$=0.32 using monoclinic space group Pm in the 2$`\theta `$ range 20 to 60 degrees. Inset shows the patterns in the 2$`\theta `$ range 60 to 120 degrees. Tick marks above the difference profle show peak positions for CuK$`\alpha 1`$.

Fig.8 Observed (dots), calculated (continuous line) and difference (bottom line) profiles obtained after the Rietveld refinement of PMN-$`x`$PT with $`x`$=0.39 using tetragonal space group P4mm in the 2$`\theta `$ range 20 to 60 degrees. Inset shows the patterns in the 2$`\theta `$ range 60 to 120 degrees. Tick marks above the difference profle show peak positions for CuK$`\alpha 1`$.

Fig.9 Variation of molar fractions of different phases with composition (x) as obtained by Rietveld refinement.

Fig.10 Variation of lattice parameters with composition (x) for the majority phases of PMN-xPT.

Fig.11 Phase diagram for ferroelectric perovskites in the space of the dimensionless parameters $`\alpha `$ (vertical axis) and $`\beta `$ (horizontal axis) \[after Ref. \]

Table 1. Refined structural parameters of PMN-$`x`$PT for $`x`$=0.20 and 0.26 using rhombohedral space group R3mH.

| composition |  |  |  |  | Ions |  |  |  | Positional coordinates |  | Thermal parameters |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |

| (x) |  |  |  |  | X | Y | Z |  |  |  | B($`\AA ^2`$) |  |  |  |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |
| 0.20 |  |  |  | $`Pb^{2+}`$ | 0.00 | 0.00 | 0.542(1) |  |  |  | 3.02(1) |  |  |  |
| 0.26 |  |  |  | $`Pb^{2+}`$ | 0.00 | 0.00 | 0.546(1) |  |  |  | 2.91(2) |  |  |  |
| 0.20 |  |  |  | $`Ti^{4+}/Nb^{5+}/Mg^{2+}`$ | 0.00 | 0.00 | 0.02(2) |  |  |  | 0.61(7) |  |  |  |
| 0.26 |  |  |  | $`Ti^{4+}/Nb^{5+}/Mg^{2+}`$ | 0.00 | 0.00 | 0.019(1) |  |  |  | 0.14(4) |  |  |  |
| 0.20 |  |  |  | $`O^2`$ | 0.353(3) | 0.176(3) | 0.1667 |  |  |  | 0.0(1) |  |  |  |
| 0.26 |  |  |  | $`O^2`$ | 0.325(3) | 0.162(3) | 0.1667 |  |  |  | 0.3(1) |  |  |  |

| 0.20 |  | $`a=b=5.6921(1)`$($`\AA `$) |  |  | $`c=6.9882(2)`$ ($`\AA `$) |  |  |
| --- | --- | --- | --- | --- | --- | --- | --- |
| 0.26 |  | $`a=b=5.6841(1)`$($`\AA `$) |  |  | $`c=6.9800(1)`$ ($`\AA `$) |  |  |
| 0.20 |  | $`R_{WP}`$= 14.76 | $`R_{exp}=6.46`$ |  | $`R_B=10.12`$ | $`\chi ^2`$ =5.06 |  |
| 0.26 |  | $`R_{WP}`$= 12.98 | $`R_{exp}=7.45`$ |  | $`R_B=9.93`$ | $`\chi ^2`$ =3.01 |  |

Table 2. Refined structural parameters of PMN-$`x`$PT for $`x`$=0.29 using monoclinic space group Cm.

|  |  |  | Ions |  |  |  |  |  | Positional coordinates |  |  | Thermal parameters |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |

|  | X | Y | Z |  |  |  | B ($`\AA ^2`$) |  |  |  |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |
| $`Pb^{2+}`$ | 0.00 | 0.00 | 0.00 |  |  |  | 3.08(2) |  |  |  |
| $`Ti^{4+}/Nb^{5+}/Mg^{2+}`$ | 0.5250(8) | 0.00 | 0.498(2) |  |  |  | 0.73(4) |  |  |  |
| $`O_I^2`$ | 0.54(1) | 0.00 | -0.01(2) |  |  |  | 0.2(3) |  |  |  |
| $`O_{II}^2`$ | 0.317(2) | 0.267(4) | 0.48(1) |  |  |  | 0.3(2) |  |  |  |

| $`a=5.6951(2)`$($`\AA `$) |  | $`b=5.6813(2)`$($`\AA `$) |  | $`c=4.0138(1)`$($`\AA `$) |  | $`\beta =90.136(3)(^0)`$ |
| --- | --- | --- | --- | --- | --- | --- |
| $`R_{WP}`$= 12.24 |  | $`R_{exp}=6.46`$ |  | $`R_B=7.10`$ |  | $`\chi ^2`$ =3.59 |

Table 3. Refined structural parameters of PMN-$`x`$PT for $`x`$=0.32 using monoclinic space group Pm.

|  |  |  | Ions |  |  |  |  |  | Positional coordinates |  |  | Thermal parameters |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |

|  | X | Y | Z |  |  |  | B ($`\AA ^2`$) |  |  |  |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |
| $`Pb^{2+}`$ | 0.00 | 0.00 | 0.00 |  |  |  | 3.28 |  |  |  |
| $`Ti^{4+}/Nb^{5+}/Mg^{2+}`$ | 0.509(2) | 0.50 | 0.5479(7) |  |  |  | 0.20(3) |  |  |  |
| $`O_I^2`$ | 0.47(1) | 0.00 | 0.57(1) |  |  |  | 0.2(2) |  |  |  |
| $`O_{II}^2`$ | 0.417(8) | 0.50 | 0.059(6) |  |  |  | 0.2(2) |  |  |  |
| $`O_{III}^2`$ | -0.02(1) | 0.50 | 0.57(1) |  |  |  | 0.0(3) |  |  |  |

| $`a=4.0183(2)`$($`\AA `$) |  | $`b=4.0046(1)`$($`\AA `$) |  | $`c=4.0276(2)`$($`\AA `$) | $`\beta =90.146(3)(^0)`$ |
| --- | --- | --- | --- | --- | --- |
| $`R_{WP}`$= 10.63 |  | $`R_{exp}=5.42`$ |  | $`R_B=9.56`$ | $`\chi ^2`$ =3.84 |

Table 4. Refined structural parameters of PMN-$`x`$PT for $`x`$=0.39 using tetragonal space group P4mm.

|  |  |  | Ions |  |  |  |  |  | Positional coordinates |  |  | Thermal parameters |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |

|  | X | Y | Z |  |  |  | B ($`\AA ^2`$) |  |  |  |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |
| $`Pb^{2+}`$ | 0.00 | 0.00 | 0.00 |  |  |  | 2.92(1) |  |  |  |
| $`Ti^{4+}/Nb^{5+}/Mg^{2+}`$ | 0.50 | 0.50 | 0.532(1) |  |  |  | 0.76(4) |  |  |  |
| $`O_I^2`$ | 0.50 | 0.50 | 0.054(4) |  |  |  | 0.8(3) |  |  |  |
| $`O_{II}^2`$ | 0.50 | 0.00 | 0.601(2) |  |  |  | 0.4(2) |  |  |  |

| $`a=3.9920(0)`$($`\AA `$) |  |  | $`c=4.0516(1)`$($`\AA `$) |  |  |  |  |  |
| --- | --- | --- | --- | --- | --- | --- | --- | --- |
| $`R_{WP}`$= 13.85 |  |  | $`R_{exp}=6.75`$ |  |  | $`R_B=10.12`$ |  | $`\chi ^2`$ =4.21 |

Table5. Refined cell parameters of PMN-$`x`$PT for the majority phases in the composition range $`0.20x0.45`$.      Composition         Cell parameters

|  |  |  |  | (x) |  |  |  |  |  | a($`\AA `$) |  |  | b($`\AA `$) |  | c($`\AA `$) |  | $`\beta `$(deg.) |  |  |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |
|  |  |  |  | 0.20 |  |  |  |  |  | 5.6921(1) |  |  |  |  | 6.9882(2) |  |  |  |  |
|  |  |  |  | 0.26 |  |  |  |  |  | 5.6841(1) |  |  |  |  | 6.9800(1) |  |  |  |  |
|  |  |  |  | 0.27 |  |  |  |  |  | 5.7001(2) |  |  | 5.6852(2) |  | 4.0186(1) |  | 90.126(3) |  |  |
|  |  |  |  | 0.28 |  |  |  |  |  | 5.6975(2) |  |  | 5.6814(2) |  | 4.0159(2) |  | 90.133(3) |  |  |
|  |  |  |  | 0.29 |  |  |  |  |  | 5.6953(2) |  |  | 5.6813(2) |  | 4.0138(1) |  | 90.136(3) |  |  |
|  |  |  |  | 0.30 |  |  |  |  |  | 5.6962(3) |  |  | 5.6806(2) |  | 4.0123(2) |  | 90.131(3) |  |  |
|  |  |  |  | 0.31 |  |  |  |  |  | 4.0193(2) |  |  | 4.0082(2) |  | 4.0288(2) |  | 90.145(3) |  |  |
|  |  |  |  | 0.32 |  |  |  |  |  | 4.0183(2) |  |  | 4.0046(1) |  | 4.0276(2) |  | 90.146(3) |  |  |
|  |  |  |  | 0.33 |  |  |  |  |  | 4.0185(2) |  |  | 4.0026(1) |  | 4.0274(1) |  | 90.169(2) |  |  |
|  |  |  |  | 0.34 |  |  |  |  |  | 4.0174(2) |  |  | 4.0019(2) |  | 4.0289(2) |  | 90.177(3) |  |  |
|  |  |  |  | 0.35 |  |  |  |  |  | 4.0004(1) |  |  |  |  | 4.0464(1) |  |  |  |  |
|  |  |  |  | 0.36 |  |  |  |  |  | 3.9970(1) |  |  |  |  | 4.0468(1) |  |  |  |  |
|  |  |  |  | 0.37 |  |  |  |  |  | 3.9953(1) |  |  |  |  | 4.0492(1) |  |  |  |  |
|  |  |  |  | 0.38 |  |  |  |  |  | 3.9933(0) |  |  |  |  | 4.0495(1) |  |  |  |  |
|  |  |  |  | 0.39 |  |  |  |  |  | 3.9920(0) |  |  |  |  | 4.0516(1) |  |  |  |  |
|  |  |  |  | 0.45 |  |  |  |  |  | 3.9832(1) |  |  |  |  | 4.0579(1) |  |  |  |  |