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# Shape coexistence and tilted-axis rotation in neutron-rich hafnium isotopes

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## Abstract

We have performed tilted-axis-cranked Hartree-Fock-Bogoliubov calculations for a neutron-rich hafnium isotope (182Hf) whose proton and neutron numbers are both in the upper shell region. We study whether the shell effects play a role in producing high-$`K`$ isomers or highly gamma-deformed states at high spin. In particular, the possibility of shape coexistence and the effect of wobbling motion are discussed.

Keywords: High-$`K`$ states, gamma deformation, wobbling motion, tilted axis cranking model
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Hafnium isotopes ($`Z=72`$) are best known as nuclei that have high-$`K`$ isomers (e.g., the $`K^\pi =16^+`$ isomer in 178Hf, with a half life $`t_{1/2}=31`$ yr ). From a viewpoint of the Nilsson model, a reason is that proton single-particle levels are filled up to the upper part of the shell where there are many high-$`\mathrm{\Omega }`$ states at prolate deformation ($`\mathrm{\Omega }`$ is the angular momentum projection on the nuclear symmetry axis). The presence of long-lived high-$`K`$ isomers indicates the existence of axial symmetry to make $`K=_i\mathrm{\Omega }_i`$, a good quantum number. With recent developments of experimental techniques, such as fragmentation  and deep-inelastic reactions  in populating high-spin states, the study of nuclei in the well deformed rare-earth region moves away from the $`\beta `$ stable line towards the neutron-rich isotopes. D’Alarcao et al. recently discovered several high-$`K`$ isomers in the neutron-rich hafnium isotope of 182Hf . For neutron-rich hafnium isotopes, whose neutron Fermi level is located in a similar position to the proton one (i.e., the upper half of the shell), we can expect an even more important role for high-$`K`$ isomeric states . At the same time, however, the empty nucleon states near the Fermi surfaces can be considered as hole states, and these may induce substantial gamma deformation which breaks the axial symmetry.

A few theoretical investigations of high angular momentum collective states have been reported for such neutron-rich hafnium isotopes: by means of a microscopic method (cranked Hartree-Fock-Bogoliubov method, or C-HFB), the possibility of a collective oblate deformation at high-spin ($`I=26\mathrm{}`$) in 180Hf was predicted ; by means of a macroscopic-microscopic method (total routhian surface calculations, or TRS), the existence of non-collective prolate-deformed states becoming yrast, i.e., lowest in energy, for $`I10\mathrm{}`$ was shown in 182-186Hf . In the latter study, the collective oblate deformed states become yrast when quite high in spin ($`I=36\mathrm{}`$ in 182Hf). In both of the studies, the rotational states are treated only by the one-dimensional cranking model, but recent developments in the tilted-axis-cranking model  allow for the possibility of further investigation of these neutron-rich hafnium isotopes.

In this paper, in a microscopic framework of the two-dimensional tilted-axis-cranked HFB method, we analyze the high-spin structures predicted for the neutron-rich hafnium isotope 182Hf (which has $`N/Z=1.53`$).

First, the calculational procedure is briefly described. We solve the HFB equations with a 2d-cranking term self-consistently for 182Hf, following the method of steepest-descent . Nucleon numbers and the total angular momentum are constrained during the iterations; $`\widehat{N}_\tau =N_\tau (\tau =\mathrm{p},\mathrm{n});J_x=\widehat{I}_x=J\mathrm{cos}\theta ;J_y=\widehat{I}_y=0;J_z=\widehat{I}_z=J\mathrm{sin}\theta `$. (Note that the tilt angle $`\theta `$ is measured from the $`x`$-axis to see the deviation of the rotation axis from the $`x`$-axis. In this study, it corresponds to a principal axis of the quadrupole deformation, perpendicular to the symmetry axis that is chosen to be the $`z`$-axis). We also constrain off-diagonal components of the quadrupole tensor such that the intrinsic coordinate axes coincide with the principal axes of the quadrupole deformation. See Ref., for details.

The one-dimensional cranking calculations (or 1d-cranking calculations), in which the rotation axis is fixed to be along the $`x`$-axis ($`\theta =0^{}`$), are performed as follows. First for $`J=0`$, the Nilsson + BCS state is taken as a trial state. Then cranked HFB states, $`\mathrm{\Psi }_\mathrm{u}(J)`$, are calculated up to $`J=40\mathrm{}`$ with increments $`\mathrm{\Delta }J=0.1\mathrm{}`$. This way of calculation is what we call “up-cranking” calculations. Then, using the up-cranking solution at $`J=40\mathrm{}`$ as a trial state, “down-cranking” calculations are similarly performed from $`J=40\mathrm{}`$ down to $`J=0`$ to obtain $`\mathrm{\Psi }_\mathrm{d}(J)`$.

The calculations of tilted-axis-cranked HFB states (2d-cranked states, or $`\mathrm{\Psi }^t(J,\theta )`$) are carried out by starting at a state $`\mathrm{\Psi }^\mathrm{t}(J,\theta =0^{})`$, which are calculated through an up-cranking calculation, and performing a “forward” tilting calculation up to $`\theta =90^{}`$ with increments $`\mathrm{\Delta }\theta =0.5^{}`$ for each (integer) $`J`$. Then in a similar manner we make “backward” tilting calculations from $`\theta =90^{}`$ to $`\theta =0^{}`$. At certain tilt angles, the forward and backward tilting results do show interesting differences, particularly, at high spins.

Our Hamiltonian consists of a spherical part ($`H_0`$) and a residual part ($`V_{\mathrm{res}}`$) employing the pairing-plus-$`\mathrm{Q}\mathrm{Q}`$ interaction. In the hafnium isotopes the hexadecapole interaction can be important, but we have checked that our results below are not affected very much by including the interaction. Thus we omit it in the present study. The Hamiltonian is thus written,

$`H`$ $`=`$ $`H_0+V_{\mathrm{res}}`$ (1)
$`=`$ $`{\displaystyle \underset{\tau =\mathrm{p},\mathrm{n}}{}}{\displaystyle \underset{i=1}{\overset{N(\tau )}{}}}ϵ_ic_i^{}c_i{\displaystyle \frac{1}{2}}\kappa {\displaystyle \underset{\mu =2}{\overset{2}{}}}\widehat{Q}_\mu ^{}\widehat{Q}_\mu {\displaystyle \underset{\tau =\mathrm{p},\mathrm{n}}{}}G_\tau \widehat{P}_\tau ^{}\widehat{P}_\tau ,`$ (2)
in which $`ϵ_i`$ means a spherical Nilsson level and $`i`$ runs all over the model space. Force parameters $`\kappa `$ and $`G_\tau `$ are determined in the framework of the Nilsson + BCS model by giving input parameters for the quadrupole deformation ($`\beta ^{\mathrm{ini}},\gamma ^{\mathrm{ini}})`$ and gap energy $`(\mathrm{\Delta }_\tau ^{\mathrm{ini}}`$). (Our definition of $`\gamma `$ is taken from pp.8 in Ref., and is opposite to the Lund convention in the sign.) In this paper, we employ a set of the input parameters based on the calculations by Möller et al. because we find it gives a good agreement with experimental data. For 182Hf, we employ $`\mathrm{\Delta }_\mathrm{p}^{\mathrm{ini}}=0.725`$ MeV; $`\mathrm{\Delta }_\mathrm{n}^{\mathrm{ini}}=0.625`$ MeV; $`\gamma ^{\mathrm{ini}}=0^{}`$; $`\beta ^{\mathrm{ini}}=0.270`$ or $`0.268`$. We will see soon the reason for the two values of $`\beta ^{\mathrm{ini}}`$.

Our single-particle model space is almost the same as the choice of Kumar and Baranger  (two major shells in the spherical Nilsson model: $`N=4,5`$ for proton and $`N=5,6`$ for neutron), with two extra single-particle orbits, proton i13/2 and neutron $`j_{15/2}`$. The single particle energies are the spherical Nilsson model energies with $`A`$-dependent Nilsson parameters .

First of all, let us discuss a principal axis rotation ($`\theta =0^{}`$) in 1d- and 2d-cranking calculations. Fig.1 shows the energy spectra of one-dimensional up- and down-cranking states ( $`\mathrm{\Psi }_\mathrm{u}(J)`$ and $`\mathrm{\Psi }_\mathrm{d}(J)`$, respectively ) and the states of $`\theta =0^{}`$ in the 2d-cranked calculations,$`\mathrm{\Psi }^t(J,\theta =0^{})`$,that are obtained through the backward tilting procedure at a given value of $`J`$. They are plotted also in the inset of Fig.1 together with the known experimental values of the g-band. The g-band is well reproduced by our one-dimensional cranking calculations.

We have two kinds of 1d-cranked states plotted in Fig.1. They are calculated with the same conditions except for the initial value of $`\beta ^{\mathrm{ini}}`$. One (denoted as “A” in the graph) is obtained with the initial value of $`\beta ^{\mathrm{ini}}=0.270`$ while the other (denoted as “B”) is with $`\beta ^{\mathrm{ini}}=0.268`$. The small difference in $`\beta ^{\mathrm{ini}}`$ gives almost no difference in the wave functions at low spin $`(J16\mathrm{}`$), but it does lead to a significant difference at high spins. The sensitive dependence of the high-spin HFB solutions to $`\beta ^{\mathrm{ini}}`$ shows that the energy manifold in the variational space near the crossing regions has several local minima that are almost degenerate. The states “A” and “B” imply the possibility of band crossings As Hamamoto et al. pointed out , the validity of the cranking model is questionable in the band crossing region because of the semi-classical aspects in the model. However, the model works well outside the crossing region and could explain qualitative features near the crossing region, such as alignments. For a more acculate analysis of the crossing region, we should employ the so-called “variation-after-projection” method , the generator coordinate method , or the diabatic method . , which correspond to the regions $`17\mathrm{}J26\mathrm{}`$ and at $`22\mathrm{}J31\mathrm{}`$ respectively Note that we do not mean here that these values of the crossing angular momentum correspond exactly to the experimental values. In general, the simple self-consistent cranking calculations do not reproduce the value precisely. in the calculations, but a substantial difference between the states is seen in the gamma deformation. Before the crossing regions both of the states have $`\gamma 10^{}`$, while after the crossing regions the states “A” have near-prolate deformation with a negative gamma value ($`\gamma 10^{}`$) and the states “B” have oblate shape ($`\gamma 60^{}`$). (See Fig.2(a) for evolutions in gamma deformation for each solution). From an analysis of our numerical results, the oblate deformation is caused by the gradual alignments of both i13/2 neutrons and h11/2 protons, while, in addition to these alignments, the near-prolate deformation with $`\gamma 10^{}`$ is caused by the quick alignment of j15/2 neutrons. (Note that the neutrons in the j15/2 orbits are not part of the usual Kumar-Baranger model space). The solution “A” is reported in this paper for the first time. Xu et al. found that there is no stable minimum corresponding to this solution in their TRS calculations . However, they performed their (1d) cranking calculations for given rotational frequencies ($`\omega _x`$), while we have performed calculations for given (average) angular momentum vectors ($`J_x,J_y,J_z`$).

In a spin region $`23\mathrm{}J35\mathrm{}`$, the three kinds of states having different gamma deformations ($`\gamma \pm 10^{}`$ and $`60^{}`$) are close to each other in energy. This result implies a manifestation of shape coexistence at high spin, or multi-band crossings among bands specified by different gamma deformations (or corresponding rotational alignments).

It is interesting to see the energies for the state $`\mathrm{\Psi }^t(J,\theta =0^{})`$, which are represented by the thick solid line in Fig.1. The line has two discontinuities, at $`J=27\mathrm{}`$ and $`34\mathrm{}`$, implying two configuration changes. At lower spin ($`J26\mathrm{}`$), $`\mathrm{\Psi }^t(J,\theta =0^{})`$ follows the 1d-cranking calculations which give rise to nearly prolate shape ($`\gamma 10^{}`$ at $`J25\mathrm{}`$). Then at $`J=27\mathrm{}`$, the gamma deformation changes to $`\gamma 10^{}`$, which is the same as “A”. Finally, at $`J=34\mathrm{}`$, $`\mathrm{\Psi }^t(J,\theta =0^{})`$ changes into the same state as “B”, having oblate shape ($`\gamma 60^{}`$). The result that the states having different gamma deformation are connected by the tilted-axis-cranking solutions indicates the importance of the tilting degree of freedom ($`\theta `$) for the search for excited states near band crossings. In Fig.2(b), we show how the quadrupole deformations ($`\beta `$ and $`\gamma `$) evolve at $`J=34\mathrm{}`$ as we vary the tilt angle ($`\theta `$). The corresponding energy curves are plotted in Fig.3(a). There are three types of solutions with different gamma deformation: (i)the solution having no $`\theta `$-dependence in tilt angles for $`\theta 20^{}`$ is oblate ($`\gamma 60^{}`$); (ii)the solution which shows a tilted rotation minimum at $`\theta 10^{}`$ has negative gamma deformation ($`\gamma 10^{}`$); (iii)the solution with a minimum at $`\theta =90^{}`$, which may correspond to high-$`K`$ states, has $`0^{}\gamma 10^{}`$.

The energy difference between the states of type (i) and (ii) is roughly constant and small ($`500`$ keV), so that these two states can couple to form states with mixed deformation. The energy curves for these states are shallow in the range $`0^{}\theta 30^{}`$, so that fluctuations in the rotation axis, or wobbling motion , can be expected. However, gamma deformations for each state of type (i) and (ii) are quite constant against variation in the tilt angle up $`\theta 30^{}`$. Therefore, rather than a picture in which states of type (i) and (ii) are coupled thorough the wobbling motion, we should have a picture where they are connected possibly through $`\gamma `$ tunnelling, and where the mixed states wobble around the tilted rotation minimum at $`\theta 10^{}`$. Nevertheless, a coupling of these mixed states with states of type (iii), is possible through wobbling motion.

It is interesting to see in Fig. 3(a) the energy curve at $`J=40\mathrm{}`$ corresponding to the states of type (i) above. There are two minima at $`\theta =0^{}`$ and $`90^{}`$, but the barrier height between them is only $`50`$ keV, not visible in the plot. The corresponding deformation is collective oblate (the $`y`$-axis is the symmetry axis) and almost constant over the entire range of $`\theta `$. For a strict oblate symmetry, there would be no energy dependence on $`\theta `$. The projection of the nuclear deformation onto the $`xz`$ plane is a circle, so that there is no preference for a direction of (collective) rotation in the $`xz`$ plane. For finite triaxiality, it is important to consider wobbling motion in the $`\theta `$ direction.

From these discussions, we can deduce that the shape coexistence creates successive backbends (sudden changes in moments of inertia) in the excited rotational bands of $`\theta 0^{}`$. The first backbend, which is caused by neutron j15/2 alignment, in addition to alignments of neutron i13/2 and proton h11/2, is expected at lower spins, which corresponds to $`17\mathrm{}J26\mathrm{}`$ in our calculations. The second one, which is caused by de-alignment of the j15/2 neutrons and retaining alignments of the i13/2 neutrons and h11/2 protons, can be seen at higher spins (corresponding to $`22\mathrm{}J31\mathrm{}`$ in the calculations). According to Fig.1, the second backbend can be more pronounced than the first one. It is also possible that these two backbends are mixed together to create one giant backbend as Hilton and Mang predicted , but according to our analysis three types of gamma deformations are involved: $`\gamma \pm 10^{}`$ and $`60^{}`$.

Now, let us look at the calculated high-$`K`$ states. In Fig.1, states of $`\theta =90^{}`$, $`\mathrm{\Psi }^\mathrm{t}(J,\theta =90^{})`$, are shown with “$`+`$” symbols. These states correspond to a local minimum at $`\theta =90^{}`$ in the energy curve (see Fig.3(b)). In our calculations, this minimum starts to appear at $`J8\mathrm{}`$, and becomes the lowest minimum at $`J=12\mathrm{}`$ and at higher spins. The $`\theta =90^{}`$ minimum may be considered approximately to correspond to a high-$`K`$ state, and the corresponding $`z`$-axis cranked state, or $`\mathrm{\Psi }^\mathrm{t}(J,\theta =90^{})`$, is a simulation of nuclear rotation where single-particle angular momenta carry most of the total angular momentum. We have checked that the corresponding gamma deformation is almost zero as in Fig.2(b) which shows that there is axial symmetry for these states.

However, we should note that $`J_z(=J\mathrm{sin}\theta )`$ in the self-consistent cranking calculations is not an eigenvalue but just an expectation value, due to the rotational symmetry breaking by the mean field. Besides, in the tilted-axis-cranked HFB calculations, angular momenta are fully mixed in the sense that even a mixture among even and odd angular momenta happens. This is because the signature symmetry, a discrete subgroup ($`D_2`$) of the rotational group $`O(3)`$, is broken by tilted rotation . We should therefore keep in mind that the mean-field description of high-$`K`$ states has a certain limitation.

Remembering the above remarks, let us look at our results for $`\mathrm{\Psi }^\mathrm{t}(J,\theta =90^{})`$. The experimental energy of the isomer, which is tentatively assigned to $`K^\pi =13^+`$, is 2.572 MeV relative to the ground state energy, while the numerical values are 2.101 MeV ($`J=12\mathrm{}`$), 2.255 MeV ($`J=13\mathrm{}`$), and 2.408 MeV ($`J=14\mathrm{}`$). Deformations of $`\mathrm{\Psi }^\mathrm{t}(J=13\mathrm{},\theta =90^{})`$, are calculated to be $`\beta =0.2661`$ and $`\gamma =0.015^{}`$.

We can consider whether this isomer is yrast or not. (Experimentally, the g-band is identified only up to $`8\mathrm{}`$ ). Xu et al. calculated that the non-collective prolate state would be yrast at $`J=13\mathrm{}`$ . Our self-consistent calculations also show that $`\mathrm{\Psi }^\mathrm{t}(J,\theta =90^{})`$ is lower in energy than principal axis rotation, $`\mathrm{\Psi }^t(J,\theta =0^{})`$, for $`12\mathrm{}J34\mathrm{}`$, so that in this region the high-$`K`$ isomeric states can be favoured relative to the collective rotation.

Let us use the term “tilted rotation” for the states with local minima, with $`\theta 0,90^{}`$. At $`J=13\mathrm{}`$ (see Fig.3(b)), there is tilted rotation ($`\theta 15^{}`$) with an excitation energy of 2.593 MeV, which happens to be quite close to the experimental value of the $`K^\pi =13^+`$ isomer. Numerical deformation values for this minimum are $`\beta =0.2704`$ and $`\gamma =4.62^{}`$, that is, the shape is nearly prolate. It is possible to consider the tilted rotation to describe a rotational member of a high-$`K`$ state. However, at this angular momentum, the potential energy curve is shallow in the whole range of $`\theta `$ (see Fig.3(b)), and the barrier height is the same order of magnitude as uncertainties from the mean-field approximation. The question as to whether the high-$`K`$ state should be described as either a tilted rotation state or a $`z`$-axis cranked state $`\mathrm{\Psi }^t(J,\theta =90^{})`$ (or coupling of them) should be answered by a quantum mechanical calculation by using angular momentum projection (and/or the generator coordinate method), which we plan to study in the future. At this moment, the description of high-$`K`$ states in the framework of self-consistent tilted-axis-cranking calculations is reasonably good up to an accuracy of several hundred keV, but more detailed studies are surely necessary.

For these shallow energy curves, we can consider the wobbling motion to relate and cause transitions between high-$`K`$ isomers and low-$`K`$ states such as the g-band. For the energy curve at $`J=13\mathrm{}`$, there are three minima at $`\theta =0^{}`$ (principal axis rotation), $`\theta =15^{}`$ (tilted rotation), and $`\theta =90^{}`$ (possible high-$`K`$ states) within 600 keV. If the first minimum represents a rotational member in the g-band and the third (and/or second) minimum represents the one in a high-$`K`$ band, then the corresponding band crossing is expected to show (experimentally) a strong coupling as evidence for a realization of the wobbling motion.

In summary, we have performed tilted-axis-cranked HFB calculations for 182Hf, and investigated high-spin states near the yrast line up to $`J=40\mathrm{}`$. For our parameter set, the comparison of the experimental data for the g-band and a high-$`K`$ isomeric state ($`K^\pi =13^+`$) with our calculation gives a reasonable agreement within the framework of the mean-field approximation. With our modified single-particle model space based on Kumar-Baranger’s choice, we found a new HFB solution with near-prolate deformation ($`\gamma 10^{}`$) involving j15/2 neutron alignment at high spin ($`J17\mathrm{}`$). We discussed the possibility of shape coexistence among three states in principal axis rotation with different gamma deformation: two with near-prolate shapes ($`\gamma \pm 10^{}`$) and the other with oblate shape ($`\gamma 60^{}`$). An analysis of the possible backbends in yrare states was also given. In addition, we discussed the effect of wobbling motion as a coupling mode between low-$`K`$ and high-$`K`$ states.

M.O. would like to acknowledge with thanks support from the Japan Society for the Promotion of Science (JSPS). He also thanks Drs. N. Onishi, W. Nazarewicz, Y. R. Shimizu, and T. Nakatsukasa for useful discussions. Part of the computations have been done using the vector parallel process type super-computer, Fujitsu VPP700 at RIKEN and an Alpha workstation at Center for Nuclear Science (CNS), University of Tokyo.


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# A New Bell Inequality for Two Spin-1 Particle System

## Abstract

For a two spin-1 particles system, we derive a new Bell’s type inequality for local hidden variables model. For the singlet state for two spin-1 particles, we show that the inequality is violated while it is satisfied for the direct product state.

E-mail: HXW@chenwang.nju.edu.cn.

In 1965, Bell demonstrated that an interpretation of quantum theory in terms of local hidden-variables (LHV) is impossible, using inequalities now universally known as Bell inequalities. In 1969, Clauser $`\mathrm{𝑒𝑡}`$ $`\mathrm{𝑎𝑙}.`$  showed that these inequalities might be test exprimentally. Since then, a series of experiments, of increasing precision and making use of various atomic sources and detection arrangments, have been carried out to test one version or another of Bell inequalities . These inequalities studied are based on a $`22`$ Hilbert space. For a particle, the case that it’s dimension is more than 2 has been discussed by the famous Bell-KS theorem, which concerns the results of a (counterfactual) set of measurements on quantum state described by a vector in a three dimensional Hilbert space. They consider, for example, measurements of the squares of the three angular momentum components of a spin-1 state. They assume that the corresponding operators commute and can be measured simultaneously, providing one ”yes” and two ”no’s” to the questions ”Does the spin componet along $`\widehat{a}`$,$`\widehat{b}`$, $`\widehat{a}\times \widehat{b}`$ vanish?” for any $`\widehat{a}\widehat{b}S^2`$, the unit sphere in $`𝐑^3`$. Specker  and Bell  observed that Gleason’s theorem  implies that there can be no assignment of ”yes’s” and ”no’s” to the vector of $`S^2`$ consistent with this requirement: each triad is ”colored” with one ”yes” and two ”no’s”. Certainly, Bell-KS theorem can be viewed as a proof for the contradictions between noncontextual LHV models and quantum mechanics.

However, there are several pionts which weakened the Bell-KS theorem: first, noncontextual LHV is just a special case of a more general one discussed in Bell’s inequalities for $`22`$ Hilbert space; second, the Bell-KS theorem does not depend on the entanglement of the state, a spine -1 particle’s state is enough, while the Bell’s inequalities is not violated by a direct product state. In other words, the contradiction of LHV models and quantum mechanics should depend on the fact that the system is entangled or not; and lastly, there are recently works \[10-13\] pointed out that finite precision measurement will nullify the Bell-KS theorem, this make the Bell-KS theorem untestable since the fact that the measurements yet known have finite precision. Comparing with studying of the spin-half particles, the situation of the higher spin case is rather unsatisfying. Recently, M.Zukowski $`\mathrm{𝑒𝑡}`$ $`\mathrm{𝑎𝑙}.`$  showed that higher-dimensional two-particle entanglements are realizable via multiport beam splitters, and the results presented in their paper move the discussion on entangled higher-than-1/2 spin systems from the realm of gedanken-experiments to real expriments. Being motivated by their work, here we shall let the $`33`$ case to be considered in a way similiar to what Bell’s theorem has done for the $`22`$ case. There has been a series of works studying the case that the Hilbert dimension N for each particle is more than two. First results, in 1980-1982, suggested that the conflict between local realism and quantum mechanics diminishes with growing N \[15-17\]. In the early 1990’s Peres and Gisin \[18-19\] considered certain dichotomic observables applied to maximally entangled pairs of particles, they showed that the violation of local realism survives, while N is growing, but never exceeds the factor $`\sqrt{2}`$. Recently, D.Kaszlikowski $`\mathrm{𝑒𝑡}`$ $`\mathrm{𝑎𝑙}`$  investigated the general case of two entangled quantum systems defined in N-dimensional Hilbert spaces( they called it ”quNits”), and via a numerical linear optimization method they showed that violations of local realism are stronger for two maximally entangled quNits $`(3N9)`$ than that for two quNits and they are increase with N , while the two quNit systems is described by a special mixed state. In present paper,only the case N=3 is concerned: first we shall derive a inequality for a $`33`$ Hilbert space from locality and reality; then, using the singlet state of two spin-1 particles system, we shall show that the inequality is violated. The inequality is satisfied for the direct product state of the two spin-1 particles system.

The singlet state for two spin-1 particles are

$`|\mathrm{\Psi }={\displaystyle \frac{1}{\sqrt{3}}}(|m_1=1|m_2=1|m_1=0|m_2=0+|m_1=1|m_2=1),`$ (1)
where $`|m_i`$ denotes the eigenvetor of spin operator $`\widehat{S}`$ along the direction z, $`\widehat{S}_i(z)|m_i=m_i|m_i`$, $`(m_i=1,0,1)`$ for particle i(i=1,2). Let $`|m_i^{}`$ to be the eigenvector of $`\widehat{S}(\beta _i)`$, $`\widehat{S}(\beta _i)|m_i^{}=m_i^{}|m_i^{}`$( for simplity, we have let the directions in the x-z plane, and each direction is viewed as a rotation $`\beta `$ along the y axis), there is a connection between $`|m_i`$ and $`|m_i^{}`$

$`|m_i^{}=\mathrm{\Sigma }_{j=1}^3D_{ji}(\beta )|m_j,`$ (2)
and the rotation matrix is

$`D(\beta )=\left|\begin{array}{ccc}\frac{1+cos(\beta )}{2}& \frac{sin(\beta )}{\sqrt{2}}& \frac{1cos(\beta )}{2}\\ \frac{sin(\beta )}{\sqrt{2}}& cos(\beta )& \frac{1cos(\beta )}{\sqrt{2}}\\ \frac{1cos(\beta )}{2}& \frac{sin(\beta )}{\sqrt{2}}& \frac{1+cos(\beta )}{2}\end{array}\right|`$ (6)
With the singlet state(1) as a source, particle 1 propagates along the y axis, while particle 2 in the -y axis. A Stern-Gerlach magnetic analyzer is put in a place where particle 1 will arrive at, and it will give the results for spin projection along a direction $`\beta _1`$, while a similar analyzer, which locates a distance away from the analyzer for particle 1, is used to measure the spin projection along $`\beta _2`$ for particle 2. Now, the singlet state (1) can be written as

$`|\mathrm{\Psi }={\displaystyle \frac{1}{\sqrt{3}}}\{`$ $`\mathrm{sin}^2({\displaystyle \frac{\beta _1\beta _2}{2}})|1|1{\displaystyle \frac{1}{\sqrt{2}}}\mathrm{sin}(\beta _1\beta _2)|1|0+\mathrm{cos}^2({\displaystyle \frac{\beta _1\beta _2}{2}})|1|1`$ (9)
$`+{\displaystyle \frac{1}{\sqrt{2}}}\mathrm{sin}(\beta _1\beta _2)|0|1\mathrm{cos}(\beta _1\beta _2)|0|0{\displaystyle \frac{1}{\sqrt{2}}}\mathrm{sin}(\beta _1\beta _2)|0|1`$
$`+\mathrm{cos}^2({\displaystyle \frac{\beta _1\beta _2}{2}})|1|1+{\displaystyle \frac{1}{\sqrt{2}}}\mathrm{sin}(\beta _1\beta _2)|1|0+\mathrm{sin}^2({\displaystyle \frac{\beta _1\beta _2}{2}})|1|1\}.`$
Defining the joint probability correlation

$`P_{m_1m_2}=\mathrm{\Psi }|m_1m_1||m_2m_2|\mathrm{\Psi },(m_1,m_2=1,0,1)`$ (10)
the singlet state in the form (4) give the following joint probabilities:

$`P_{11}(\beta _1,\beta _2)={\displaystyle \frac{1}{3}}\mathrm{sin}^4({\displaystyle \frac{\beta _1\beta _2}{2}}),P_{00}+P_{0,1}+P_{1,0}+P_{11}={\displaystyle \frac{1}{3}}[1+\mathrm{sin}^4({\displaystyle \frac{\beta _1\beta _2}{2}})].`$ (11)
We should prove that the correlation (6) can not be interpreted by LHV models.

Assuming that the state(1) can be described by a set of parameters $`\lambda `$, LHV models gives the probabilities $`p_m(\beta _1,\lambda )`$ and $`q_n(\beta _2,\lambda )`$ for the two results that the spin projection along $`\beta _1`$ is m for particle 1 and the spin projection along $`\beta _2`$ is n for particle 2 respectively( m,n=1,0,-1). As a cosequence of the relation

$`|m_i=1m_i=1|+|m_i=0m_i=0|+|m_i=1m_i=1|=I,(i=1,2)`$ (12)
there is a natural conditions here

$`op_1(\beta _1,\lambda )+p_0(\beta _1,\lambda )+p_1(\beta _1,\lambda )1,`$ (13)
$`0q_1(\beta _2,\lambda )+q_0(\beta _2,\lambda )+q_1(\beta _2,\lambda )1.`$ (14)
It should be noted that $`p_m(\beta _1,\lambda )`$ does not depend on the settings of $`\beta _2`$ , while $`q_n(\beta _2,\lambda )`$ is not depending on $`\beta _1`$ either. They are required by the locality assumption, which aserts that experiments done on one place have no influence on the resluts of measurement done on the other place located a distance away if two measurements are performed simultaneously, and the joint probability should be

$`P_{mn}(\beta _1,\beta _2)={\displaystyle _{\lambda \mathrm{\Lambda }}}p_m(\beta _1,\lambda )q_n(\beta _2,\lambda )\rho (\lambda )𝑑\lambda ,`$ (15)
while

$`{\displaystyle _{\lambda \mathrm{\Lambda }}}\rho (\lambda )𝑑\lambda =1.`$ (16)
In order to derive a inequality, we use the following simple algebraic theorem: giving six real numbers x,x’,X,y,y’ and Y, such that $`0x,x^{}X,0y,y^{}Y`$ one must always have

$`XYxyxy^{}+x^{}y+x^{}y^{}x^{}YXy0`$ (17)
The proof of it has been given by Clauser and Horne . Making the identifications $`x=p_1(\beta _1,\lambda ),x^{}=p_1(\beta _1^{},\lambda ),y=q_1(\beta _2,\lambda ),y^{}=q_1(\beta _2^{},\lambda )`$, and taking X=Y=1(since the natural conditions), one can obtain

$`p_1(\beta _1,\lambda )q_1(\beta _2,\lambda )p_1(\beta _1,\lambda )q_1(\beta _2^{},\lambda )+p_1(\beta _1^{},\lambda )q_1(\beta _2^{},\lambda )`$ (18)
$`+(p_0(\beta _1^{},\lambda )+p_1(\beta _1^{},\lambda ))(q_o(\beta _2,\lambda )+q_1(\beta _2,\lambda ))1,`$ (19)
through using the natural conditions$`(8)`$. Intergrating over $`\rho (\lambda )`$, a inequality for $`33`$ Hilbert space can be dereived :

$`S=P_{11}(\beta _1,\beta _2)P_{11}(\beta _1,\beta _2^{})+P_{11}(\beta _1^{},\beta _2^{})`$ (20)
$`+P_{00}(\beta _1^{},\beta _2)+P_{01}(\beta _1^{},\beta _2)`$ (21)
$`+P_{10}(\beta _1^{},\beta _2)+P_{11}(\beta _1^{},\beta _2)1.`$ (22)
It can be easily shown tha this inequality will be violated by the quantum joint probability given in eq.(6). Choosing the following sets of the angles $`\beta _1=0`$,$`\beta _1^{}=2\beta _2`$, $`\beta _2^{}=3\beta _2`$, and $`\beta _2=147.7`$degree, we get a contradiction

$`S=1.121.`$ (23)
Certainly, the above S is less than the factor 4/3 given in case of the multiport beam splitter.

If the state is a direct product state, for example

$`|\mathrm{\Psi }^{}=|1|0,`$ (24)
now the probability is

$`P_{11}(\beta _1,\beta _2)=\mathrm{cos}^4{\displaystyle \frac{\beta _1}{2}}\mathrm{sin}^4{\displaystyle \frac{\beta _2}{2}},P_{00}={\displaystyle \frac{1}{4}}\mathrm{sin}^2\beta _1\mathrm{sin}^2\beta _2,P_{0,1}={\displaystyle \frac{1}{2}}\mathrm{sin}^2\beta _1\mathrm{cos}^4{\displaystyle \frac{\beta _2}{2}},`$ (25)
$`P_{1,0}={\displaystyle \frac{1}{2}}\mathrm{cos}^4{\displaystyle \frac{\beta _1}{2}}\mathrm{sin}^2\beta _2,P_{1,1}=\mathrm{sin}^4{\displaystyle \frac{\beta _1}{2}}\mathrm{cos}^4{\displaystyle \frac{\beta _2}{2}},`$ (26)
then, we have the following form

$`S=\mathrm{cos}^4{\displaystyle \frac{\beta _1}{2}}\mathrm{sin}^4{\displaystyle \frac{\beta _2}{2}}\mathrm{cos}^4{\displaystyle \frac{\beta _1}{2}}\mathrm{sin}^4{\displaystyle \frac{\beta _2^{}}{2}}+\mathrm{cos}^4{\displaystyle \frac{\beta _1^{}}{2}}\mathrm{sin}^4{\displaystyle \frac{\beta _2^{}}{2}}+(1\mathrm{cos}^4{\displaystyle \frac{\beta _1^{}}{2}})(1\mathrm{sin}^4{\displaystyle \frac{\beta _2}{2}}),`$ (27)
while the ineqality (11) can be transfered into a form

$`xyxy^{}+x^{}y^{}+(1x^{})(1y)1.`$ (28)
Comparing the above two forms, we know that $`S1`$ is always satisfied for direct product state and has no relation to the directions chosen.

In conclusion, for the $`33`$ Hilbert space, we have derived a inequality as Bell’s inequality for the $`22`$ case. For the singlet state for two spin-1 particles system, we show that the inequality will be violated while it is valid for the case when the two particle in a direct product state.

This work is supported by the NSF,SED,SSTD of China.


text:
# Coherent description of electrical and thermal impurity–and–phonon limited transport in simple metals

## I Introduction

To consider the most simple models is sometimes necessary for studying the charge carrier and thermal transport in solids. Indeed mathematical approximations used on more sophisticated models may make less evident, or even completely suppress, certain effects. For the transport coefficients the latter statement surely concerns the thermoelectric power and the thermal conductivity. For studying the electrical resistivity theoretical methods are surely simpler, better developed and more reliable.

When there is more than a single scattering source the electrical resistivity is sufficiently accurately treated in metals under the assumption of Matthiessen rule  (see exceptions in Concluding Remarks). Further assumptions are necessary to find simple and effective expressions for the thermoelectric power and the thermal conductivity. The Gorter–Nordheim rule, which is usually applied to treat the thermoelectric power, is based on the assumption of the Mott(-Jones) formula validity, however, restricted to the elastic scattering  and the adiabatic approximation . For the thermal conductivity the Wiedemann–Franz law is a usual basis on which the separation of the electronic and lattice contribution to the experimental thermal conductivity is made, whence for comparing experimental and theoretical data. The validity of the Wiedemann–Franz law is also restricted to elastic collisions. Clearly to resolve the question of elasticity and inelasticity of the scattering is essential for comparing experimental data and theoretical laws in particular for the thermoelectric power and the thermal conductivity.

The most simple inelastic scattering model of the charge carriers by phonons describes most features  of the thermoelectric power in normal metals. Consequently, an approach well accounting for the energy transfer between the charge carriers and the scattering quasiparticles should be applied beyond that based on the Mott formula .

It is known that the elastic approximation is sufficient for considering the scattering of the conduction electrons by static impurities. This leads to a constant, temperature independent residual resistivity, when the potential is appropriately chosen and the electron gas is degenerate. The simplest and well founded potential which leads to the residual resistivity in metals is the screened Coulomb potential (or Yukawa potential) provided that impurity concentration is sufficiently low.

Phenomenological considerations  show that without assuming a behavior for the electrical residual resistivity one cannot explain the low temperature behavior of the electronic contribution to the thermal conductivity. At moderate temperatures, along with the scattering by phonons the impurity scattering explains the magnitude and the basic features of the temperature dependence of the thermal conductivity of normal nonmagnetic  and even magnetic  metals, provided that the magnetic moment in the latter is periodic and well localized. It was shown indeed in Ref., devoted solely to the thermal conductivity, $`\kappa `$, that the magnetic scattering was of equal importance to the impurity and the phonon scattering. However, $`\kappa `$ was neither compared to the electrical resistivity $`\rho `$, nor to the thermoelectric power $`S`$, for example calculated in the same temperature interval in Ref.. Moreover the final results were not presented through standard functions such as the Bloch–Grüneisen ones. We shall do so in the present paper, but confining ourselves to non magnetic impurity and phonon scattering only.

As in our previous papers we shall apply the Ziman variational approach  within the Boltzmann equation formalism, an approach in which the notion of ”relaxation time” is not used. Thus, the relationship to the Mott formula is not straightforward . However, terms responsible for elastic and inelastic scattering can be easily selected, at least when the conduction band is parabolic. Within this approach one can generalize the Matthiessen rule: we consider a superposition of the transition probabilities themselves within the Boltzmann equation formalism  instead of the (integrated) relaxation time components. Therefore the electrical resistivity, the thermoelectric power and the thermal conductivity are considered here with respect to impurity and phonon scattering on the same ground, i.e. both model and approximations. For this purpose it is sufficient to introduce a single parameter which accounts for the mutual contribution of the phonon and the impurity scattering to the transport coefficients.

A similar model accounting for the scattering by phonons and impurities was considered in the fifties  within the Kohler variational formalism . However, the mathematical method was more complicated and less physical than that developed later by Ziman . It did not allow  to get qualitatively correct results for the thermoelectric power in contrast to those for the electrical resistivity and the electronic thermal conductivity.

The finding of an accurate solution of the (Bloch–)Boltzmann equation is not a past problem of the fifties or the seventies but still a present–day problem. Numerical methods are used for this purpose. Recently  the Allen method  of solving the equation with a good numerical convergence has been used to study the influence of the electron–electron scattering on the electrical and thermal conductivity. A comparative discussion of the approximation made while using the Ziman variation method  and the Allen one  is given in Sec.V.

In the following Section II we shortly describe the Ziman variational method and the general results when applied to the model here defined. Certain general results and formulae are also given in Appendix A for completeness. In Section III the matrix elements describing the phonon and impurity scattering are calculated and final formulas for the electrical resistivity, electronic thermal conductivity and thermoelectric power are systematically presented. In Section IV the temperature dependence of the transport coefficients and that of the Lorenz number is numerically illustrated. The visual presentation is made by using dimensionless functions. An analysis of appropriate material constants allowing to estimate the magnitude of the final transport coefficients is found in Appendix B. Section V contains the concluding remarks.

## II Model, method and approximations.

We assume that the current carriers are free electrons with a parabolic isotropic energy band $`\epsilon (𝐤)=\mathrm{}^2𝐤/2m`$ spectrum. We also assume that the concentration of the electron gas (of both subbands with spin up or down) $`n_e=(1/3\pi ^2)(2m/\mathrm{}^2)^{3/2}\epsilon _{\mathrm{F}}^{}{}_{}{}^{3/2}`$ (or the Fermi energy $`\epsilon _\mathrm{F}`$) is sufficiently high to consider the gas to be degenerate. Then one can assume that the chemical potential is $`\zeta (T)\epsilon _\mathrm{F}`$, and all relevant functions of $`z=\zeta /k_\mathrm{B}T`$ can be considered as asymptotic expressions of the argument $`\epsilon _\mathrm{F}/k_\mathrm{B}T`$ . In particular the Fermi-Dirac integrals

$$F_n(z)=_0^{\mathrm{}}dx\frac{x^n}{1+\mathrm{exp}[xz]},\text{ }\mathrm{with}\text{ }z=\frac{\zeta (T)}{k_\mathrm{B}T}$$
(1)
can be represented as

$$F_n(z)z^{n+1}/(n+1),\text{ }\mathrm{with}\text{ }z\epsilon _\mathrm{F}/k_\mathrm{B}T$$
(2)
for sufficiently large $`z`$.

The carriers are assumed to be scattered by static, nonmagnetic impurities, which concentration is sufficiently low to have a linear influence on the electrical resistivity . The scattering of carriers by phonons will be considered on the same footing. However, the phonon (quasiparticle) scattering will be treated as inelastic while the impurity scattering is elastic in its nature, since the impurity is usually assumed to be more heavy than the electron effective mass. Even though some calculations can be performed without assuming the form of the potential) we assume the form of the impurity potential to be the screened (Yukawa) potential

$$U(𝐫)=\frac{Ze^2\mathrm{exp}(\lambda r)}{r}$$
(3)
with $`r=|𝐫|`$, $`Z=Z_{impurity}Z_{hostion}`$ the effective valence and the screening constant $`\lambda `$. The Fourier transform $`U(𝐪)=4\pi Ze^2/(\lambda ^2+𝐪^2)`$ of the above function is responsible for the magnitude of the carrier scattering; $`𝐪`$ with $`q|𝐪|`$ is the electron wave vector transferred during the scattering. The transport relaxation time following from $`U(𝐪)`$ – and consequently the residual resistivity – is temperature independent for a degenerate electron gas. Their magnitude is related to the Fermi wave vector $`k_\mathrm{F}`$ or the energy $`\epsilon _\mathrm{F}`$ through the function

$$2_0^{2k_\mathrm{F}}\frac{\mathrm{d}qq^3}{(\lambda ^2+q^2)^2}=\mathrm{ln}(1+4k_{\mathrm{F}\lambda }^2)4k_{\mathrm{F}\lambda }^2/(1+4k_{\mathrm{F}\lambda }^2)\mathrm{\Phi }(2\mathrm{k}_{\mathrm{F}\lambda }),$$
(4)
where $`k_{\mathrm{F}\lambda }=k_\mathrm{F}/\lambda `$ .

Note that the standard considerations  yield that $`\lambda ^2n_{e}^{}{}_{}{}^{1/3}`$ and thus one can estimate $`2k_\mathrm{F}=(3\pi )^{1/6}(a_Hk_\mathrm{F})^{1/2}1`$ since the effective Bohr radius $`a_H=\mathrm{}/(me^2)`$ is of the order of $`k_\mathrm{F}`$.

The phonon system and the electron–phonon scattering are considered in the Bloch approximation, i.e. phonons in the harmonic approximation and the electron–phonon interaction in the deformation potential approximation. We restrict the magnitude of the phonon wave vector, $`qq_D`$, to be within the Debye sphere. Then, for sufficiently high values of the Fermi energy, $`z=\mathrm{}`$ (see,e.g., Appendix B in Ref.), the phonon limited transport coefficients are expressed in terms of the Bloch(–Grüneisen) functions

$$_n(t)=\underset{0}{\overset{1//t}{}}\frac{dxx^n}{(\mathrm{e}^x1)(1\mathrm{e}^x)}.$$
(5)
A relation between the deformation potential approximation and the method based on the dynamical structure factor introduced by van Hove  is described in Sec. V.

As we mentioned in the Introduction we apply the Ziman variation method  to consider the combined effect of the impurity and phonon scattering on the transport coefficients. The method consists in calculating the elements of a matrix describing the scattering and two vectors governing the flow of the electric charge and heat. The ”exact” results correspond to an infinite order matrix and infinite dimension current vectors (see, e.g. Appendix A and Sec. IV in Ref.). Here, we truncate the matrix and vectors to four elements and two components, respectively. This is the lowest order approximation, which accounts well for both the electrical and thermal current if the variational trial functions are appropriately chosen. This choice is known to be

$$\mathrm{\Omega }_\mathrm{i}(𝐤)=(𝐯𝐚)(\epsilon \zeta )^{\mathrm{i}1},$$
(6)
where $`i=1`$ and $`2`$, while $`𝐚`$ denotes the unit vector in the direction of the applied temperature gradient or that of the external electric field causing the charge flow, and $`𝐯=(\mathrm{}/m)_k\epsilon `$ is the electron velocity.

In this approximation the transport coefficients : the electrical resistivity $`\rho `$, the thermoelectric power or the Seebeck coefficient $`S`$ and the (electronic) thermal conductivity $`\kappa `$ for cubic crystals, are given as such

$$\rho =(P_{11}P_{22}P_{12}^2)\mathrm{\Pi }^1,$$
(7)
$$S=[P_{22}J_1U_2P_{12}(J_1U_2+J_2U_1)+P_{11}J_2U_2](T\mathrm{\Pi })^1$$
(8)
$$\kappa =(J_1^2U_2^2+J_2^2U_1^22J_1J_2U_1U_2)(T\mathrm{\Pi })^1.$$
(9)
with

$$\mathrm{\Pi }=\mathrm{P}_{22}\mathrm{J}_1^22\mathrm{P}_{12}\mathrm{J}_1\mathrm{J}_2+\mathrm{P}_{11}\mathrm{J}_2^2,$$
(10)
the elements of the scattering matrix being

$`P_{ij}`$ $`=`$ $`{\displaystyle d𝐤d𝐤^{}C(𝐤,𝐤^{})u_{ij}(𝐤,𝐤^{})},`$ (11)
$`u_{ij}(𝐤,𝐤^{})`$ $`=`$ $`[\mathrm{\Omega }_i(𝐤)\mathrm{\Omega }_i(𝐤^{})][\mathrm{\Omega }_j(𝐤)\mathrm{\Omega }_j(𝐤^{})],`$ (12)
and the components of the trial currents ***The factor (v.a) in the expression for the trial currents in Ref. 5 was inadvertently omitted. In the trial functions (12)-(13) this factor is used as in Ref. 2, and in our previous papers where it was denoted (k.a).

$$J_i=ed𝐤\left(\frac{\mathrm{d}f}{\mathrm{d}\epsilon }\right)(𝐯𝐚)\mathrm{\Omega }_i(𝐤),$$
(13)
$$U_i=d𝐤\left(\frac{\mathrm{d}f}{\mathrm{d}\epsilon }\right)(𝐯𝐚)(\epsilon \zeta )\mathrm{\Omega }_i(𝐤),$$
(14)
where $`C(𝐤,𝐤^{})`$ is the transition probability to be determined on the ground of an appropriate Hamiltonian describing the scattering. The function $`f`$ denotes the Fermi–Dirac one, $`f=1/[1+\mathrm{exp}(\epsilon \zeta )/k_\mathrm{B}T]`$, and $`e(e>0)`$ is the electron charge.

The integrals in (11) and (13)-(14) should be taken over the Brillouin zone but in our free electron considerations we let

$$d𝐤\mathrm{}\frac{2}{(2\pi )^3}\underset{0}{\overset{\mathrm{}}{}}d\epsilon \left(\frac{\mathrm{d}S_\epsilon }{|_k\epsilon |}\right)\mathrm{},$$
(15)
where $`\mathrm{d}S_\epsilon /|_k\epsilon |`$ is an element of the isoenergy surface. The integrals with respect to the electron energy in (10) for the degenerate electron gas are described in Appendix B of Ref. 8. In the case of elastic scattering by impurities, as here, the integrals can be treated as simply. Namely, we take advantage of the approximate equalities

$$\underset{0}{\overset{\mathrm{}}{}}d\epsilon (\mathrm{d}f/\mathrm{d}\epsilon )(\epsilon \zeta )g(\epsilon )=(\pi ^2/3)(k_\mathrm{B}T)^2[\mathrm{d}g/\mathrm{d}\epsilon ]_\zeta ,$$
(16)
$$\underset{0}{\overset{\mathrm{}}{}}d\epsilon (\mathrm{d}f/\mathrm{d}\epsilon )(\epsilon \zeta )^2g(\epsilon )=(\pi ^2/3)(k_\mathrm{B}T)^2g(\zeta ).$$
(17)
where $`g(\epsilon )`$ is an arbitrary function.

The trial currents (13)-(14) can be represented  as acombination of the Fermi–Dirac integrals (see Appendix B) : $`J_1=J_0(k_\mathrm{B}T)^{3/2}L_0(z)`$, $`J_2=J_0(k_\mathrm{B}T)^{5/2}L_1(z)`$, $`U_1=U_0(k_\mathrm{B}T)^{5/2}L_1(z)`$, $`U_2=U_0(k_\mathrm{B}T)^{7/2}L_2(z)`$, where $`U_0`$ and $`J_0=eU_0`$ are material constants.

For the electron–phonon system the $`P`$–matrix elements can be derived (see Ref.) without any further approximation. They are expressed by double integrals with respect to the electron energy and the transferred electron momentum (wave vector). For a Debye cutoff and in the limit $`z\mathrm{}`$ they can be representedFor further convenience, the factor $`t^5`$ used in Ref.8 is introduced here directly in the definition of $`𝒫_{ij}`$. by $`P_{ij}=P_0(k_\mathrm{B}T)^{i+j2}𝒫_{ij}`$, where $`P_0`$ is a material constant and $`𝒫_{ij}=𝒫_{ij}(t)`$ are dimensionless combinations of the the Bloch–Grüneisen functions of the argument $`t=T/T_D`$ ($`T_D`$ is the Debye temperature).

For the impurity scattering an expression similar to the above is readily obtained. In this case the $`𝒫_{ij}`$ ’s are simply related to $`\mathrm{\Phi }(2\mathrm{k}_\mathrm{F}/\lambda )`$ defined in (4). The explicit form of the functions $`𝒫_{ij}`$ will be given in the next Section. The magnitude of $`P_0`$ and that of other material constants are estimated in Appendix B.

In view of the above, by calculating the scattering matrix elements in the degenerate limit, retaining only $`𝒫_{11}(𝒫_{12}^2/𝒫_{22})`$ in case of the electrical resistivity and the lowest order terms in the $`1/z`$ in the trial currents (12)-(13), we obtain

$$\rho =\frac{P_{11}}{J_1^2}=\frac{P_0𝒫_{11}}{J_0^2\epsilon _{\mathrm{F}}^{}{}_{}{}^{3}},$$
(18)
$$S=S_0(t)+S_1(t)\frac{k_\mathrm{B}T}{\epsilon _\mathrm{F}},$$
(19)
$$\frac{1}{\kappa }=\frac{P_{22}}{(\pi ^2/3)_0T(k_\mathrm{B}T)^3J_1^2}=\frac{P_0}{U_0^2}\frac{T𝒫_{22}}{(\pi ^2/3)^2(k_\mathrm{B}T)^2\epsilon _{\mathrm{F}}^{}{}_{}{}^{3}},$$
(20)
where $`J_1`$ in (18) and (20) is the trial current in its asymptotic form and $`_0=(\pi ^2/3)(k_\mathrm{B}/e)^2`$ is the Sommerfeld value of the Lorenz number. The explicit form of the functions $`S_0(t)`$ and $`S_1(t)`$ of (19) – having a more complicated dependence on the matrix elements $`𝒫_{ij}`$ – are discussed in Section III B.

## III Scattering matrix contributions.

As seen from (18)-(20) it remains to calculate the elements of the $`P`$–matrix in order to find the final expressions for the transport coefficients. In our case the crux is to take into account the combined effect of the scattering by impurities and phonons.

As we mentioned in the Introduction we apply the Matthiessen rule in a more generalized way , i.e. to the microscopic transition probabilities C(k,k’) themselves appearing in Eq.(11) rather than to the final coefficients: the electrical and thermal resistivity. The variational method enables us to use the same approximation to both these coefficients and the thermoelectric power through the integrated probabilities, i.e, we assume

$$C(𝐤,𝐤^{})=C^{(imp)}(𝐤,𝐤^{})+C^{(ph)}(𝐤,𝐤^{}).$$
(21)
This means that the resultant scattering probability for the phonon and impurity scattering can be simply considered as a sum of the scattering probabilities of the impurities (the phonon scattering being quenched) and by phonons (those of the pure crystal). This, of course, implies that the elements of the resultant scattering matrix, (11), are also the sums of the corresponding matrix elements for the phonon and impurity scattering. Therefore, we write

$$P_{ij}=P_{ij}^{(imp)}+P_{ij}^{(ph)}.$$
(22)
in formulae (7) - (9).

The electron-phonon contribution $`P_{ij}^{(ph)}`$’s have been derived in previous papers, e.g., in Ref.  they are expressed in terms of the Bloch(-Grüneisen) functions (5). The appropriate expressions for the electron-impurity contribution $`P_{ij}^{(imp)}`$ following from the Yukawa potential (3) are given in this Section, but first we write down the final expression for the electronic thermal conductivity with the influence of the residual electrical resistivity as a parameter. For this purpose we have to separate elastic and inelastic contribution to $`P_{22}`$ and therefore we write explicitly the matrices $`u_{ij}`$ of the kernels in (10). For the parabolic band $`\epsilon (𝐤)=\mathrm{}^2𝐤/2m`$ they can be represented as

$`u_{11}`$ $`=`$ $`(\mathrm{}/m)^2(𝐪𝐚)^2,`$ (23)
$`u_{12}=u_{21}`$ $`=`$ $`(\mathrm{}/m)^2[(\epsilon \zeta )+(\epsilon ^{}\epsilon )](𝐪𝐚)^2,`$ (24)
$`u_{22}`$ $`=`$ $`(\mathrm{}/m)^2[(\epsilon \zeta )^2+2(\epsilon ^{}\epsilon )(\epsilon \zeta )](𝐪𝐚)^2+(\epsilon ^{}\epsilon )^2[(𝐪𝐚)^2+(𝐤𝐚)^2].`$ (25)
where ($`\epsilon \epsilon `$) is the transferred energy during the scattering, $`𝐪=𝐤^{}𝐤`$ is the transferred wave vector and terms linear in $`𝐤`$ and $`𝐤^{}`$, which do not contribute to the integrals, have been neglected. It is seen that the second component in $`u_{12}`$ and the second and third one in $`u_{22}`$ contribute only when a change of the electron energy in the scattering is taken into account. It means that the latter terms describe the effects of inelasticityThese terms describe the basic inelastic contribution. For the phonon scattering the single term of $`u_{11}`$ and the first terms in the case of $`u_{12}`$ and $`u_{22}`$ are expressed by the Debye functions in case of pure elastic scattering and by the Bloch(-Grüneisen) functions in case of inelastic scattering (see Ref.8). The terms proportional to $`(\epsilon ^{}\epsilon )`$ and $`(\epsilon ^{}\epsilon )^2`$ in $`u_{12}`$ and $`u_{22}`$ lead to an essential qualitative effect in the thermoelectric power and the thermal conductivity. in the scattering. With the definition

$$P_{11}^{(ph)}=P_0^{(ph)}𝒫_{11}^{(ph)}(t),\mathrm{with}t=T/T_D$$
(26)
and where $`P_0^{(ph)}`$ is a material constant (see Appendix B), we get

$$P_{22}^{(ph)}=P_0^{(ph)}(k_\mathrm{B}T)^2[𝒫_{22}^{(1,ph)}(t)+𝒫_{22}^{(2,ph)}(t)]P_{22}^{(1,ph)}+P_{22}^{(2,ph)},$$
(27)
where

$`𝒫_{22}^{(1,ph)}(t)`$ $`=`$ $`{\displaystyle \frac{\pi ^2}{3}}𝒫_{11}^{(ph)}(t),`$ (28)
$`𝒫_{22}^{(2,ph)}(t)`$ $`=`$ $`t^5[{\displaystyle \frac{1}{3}}_7(t)+{\displaystyle \frac{\epsilon _s\epsilon _\mathrm{F}}{(k_\mathrm{B}T)^2}}_5(t){\displaystyle \frac{\epsilon _s}{2k_\mathrm{B}T}}_6(t)],`$ (29)
and $`\epsilon _s`$ is a constant (see Appendix B).

The explicit form of $`P_{11}^{(ph)}(t)`$ describing the electrical resistivity is

$$𝒫_{11}^{(ph)}(t)=t^5_5(t).$$
(30)
The two terms in $`u_{12}`$, accounting respectively for the elastic and inelastic contributions, after integration with the transition probability for the phonon scattering can be represented by a single term,

$$P_{12}^{(ph)}=P_{21}^{(ph)}=P_0^{(ph)}(k_\mathrm{B}T)𝒫_{12}^{(ph)}(t)$$
(31)
with

$$𝒫_{12}^{(ph)}(t)=𝒫_{21}^{(ph)}(t)=\frac{1}{2}t^5_6(t).$$
(32)
Two material constants influence the magnitude of $`𝒫_{22}^{(2,ph)}(t)`$. These are the Fermi energy, $`\epsilon _\mathrm{F}`$, and $`\epsilon _s=2mv_s^2`$, where $`v_s`$ is the sound velocity (see the Table I in Appendix). The latter energy (or more precisely $`\epsilon _s/4`$) is a threshold energy for the phonon emission in the electron–phonon scattering process (see Appendix J in Ref.).

Assume now that the charged (static) impurity concentration is so low that one can consider them to be statistically independent. Then the scattering of the conduction electrons by a single impurity contributes solely to the $`P_{ij}`$ matrix elements and they are linear in their concentrations. In consequence the electrical resistivity is linear in the electron concentration and for the degenerate electron gas it is also temperature independent.

The latter statement can be easily confirmed by the calculation of $`P_{11}^{(imp)}`$ in the metallic limit. For further convenience we assume $`P_{11}^{(imp)}/P_0^{(ph)}\mathrm{\Gamma }`$ and due to the Sommerfeld expansion of terms of (23) corresponding to an elastic scattering we have $`P_{22}^{(imp)}=P_{22}^{(imp,1)}=P_0^{(ph)}(\pi ^2/3)(k_\mathrm{B}T)^2\mathrm{\Gamma }`$. Therefore, the final expressions for $`P_{11}`$ and $`P_{22}`$ describing the impurity and phonon scattering are

$`P_{11}=P_0^{(ph)}𝒫_{11}(t),\text{ }\mathrm{with}\text{ }𝒫_{11}(t)=P_0^{(ph)}[\mathrm{\Gamma }+𝒫_{11}^{(\mathrm{p}\mathrm{h})}(\mathrm{t})]`$ (33)
$`P_{22}=P_0^{(ph)}(k_\mathrm{B}T)^2𝒫_{22}(t),\text{ }\mathrm{with}\text{ }𝒫_{22}(t)={\displaystyle \frac{\pi ^2}{3}}[\mathrm{\Gamma }+𝒫_{11}^{(\mathrm{p}\mathrm{h})}(\mathrm{t})]+𝒫_{22}^{(2,\mathrm{p}\mathrm{h})}(\mathrm{t}).`$ (34)
### A Electrical resistivity and thermal conductivity in metals

The above expressions for the matrix elements of the $`P`$–matrix yield the electrical resistivity

$$\rho =\rho _{0,ph}[\mathrm{\Gamma }+𝒫_{11}^{(\mathrm{p}\mathrm{h})}(\mathrm{t})],$$
(35)
where $`\rho _{0,ph}`$ is a constant (see Appendix B), and the electronic thermal conductivity

$$\kappa =\kappa _{0,ph}\frac{t}{𝒫_{22}(t)},\text{ }\kappa _{0,ph}=\frac{\pi ^2}{3}\frac{_0T_D}{\rho _{0,ph}}.$$
(36)
Note that the Lorenz number reads

$$=\frac{\rho \kappa }{T}=_0\frac{\pi ^2}{3}\frac{𝒫_{11}(t)}{𝒫_{22}(t)}$$
(37)
and reduces to the Sommerfeld value $`_0`$ for elastic scattering, when one neglects $`𝒫_{22}^{(2,ph)}`$ in (25).

The results (26) describing the electrical resistivity are obviously standard ones and do not require any comments. As concerns the electronic thermal conductivity and the Lorenz number similar expressions in terms of the Bloch–Grüneisen functions as those in the present paper were obtained by Wilson  and were numerically examined in Ref.  manifesting the influence of the impurity scattering. The Wilson expression for the thermal resistivity in our notation reads

$$\frac{2\pi ^3}{3}t^5_5(t)+\frac{8\pi ^2\epsilon _s\epsilon _\mathrm{F}}{(k_\mathrm{B}T)^2}t^5_5(t)\frac{1}{3}t^5_7(t).$$
(38)
### B Seebeck coefficient of metals.

In order to discuss the thermoelectric power, $`S`$, we introduce, as for the discussion of the thermal conductivity in Ref., a relative order of magnitude parameter $`\phi =P_0^{(imp)}/P_0^{(ph)}`$, in terms of which for the Yukawa potential (3) we have $`\mathrm{\Gamma }(\epsilon _\mathrm{F})=\phi \mathrm{\Phi }(2\mathrm{k}_\mathrm{F}/\lambda )`$. It will be also convenient to introduce here the function $`\mathrm{\Psi }(\mathrm{x})=\mathrm{x}^4/(1+\mathrm{x}^2)^2`$ in terms of which we express $`[\mathrm{d}\mathrm{\Phi }/\mathrm{d}\epsilon ]_{\epsilon _\mathrm{F}}=(\epsilon _\mathrm{F})^1\mathrm{\Psi }(2\mathrm{k}_\mathrm{F}/\lambda )`$ . In so doing the off-diagonal component of the $`P`$–matrix responsible for the impurity scattering is linear in $`k_\mathrm{B}T/\epsilon _\mathrm{F}`$ and reads

$$P_{12}^{(imp)}(T)=P_0^{(imp)}(k_\mathrm{B}T)𝒫_{12}^{(imp)},\text{ }𝒫_{12}^{(imp)}=\frac{\pi ^2}{3}\phi \mathrm{\Psi }(2\mathrm{k}_\mathrm{F}/\lambda )\frac{\mathrm{k}_\mathrm{B}\mathrm{T}}{\epsilon _\mathrm{F}}.$$
(39)
When these expressions are inserted into (8) and linear terms in $`k_\mathrm{B}T/\epsilon _\mathrm{F}`$ are only accounted for, one obtains the following expressions for the coefficients in (19)

$`S_0(t)={\displaystyle \frac{\pi ^2}{3}}{\displaystyle \frac{k_\mathrm{B}}{e}}{\displaystyle \frac{𝒫_{12}^{(ph)}(t)}{𝒫_{22}(t)}},\text{ }S_1(t)={\displaystyle \frac{k_\mathrm{B}}{e}}\left\{{\displaystyle \frac{\pi ^2}{2}}\left[1+{\displaystyle \frac{\pi ^3}{3}}{\displaystyle \frac{𝒫_{11}(t)}{𝒫_{22}(t)}}\right]({\displaystyle \frac{\pi ^3}{3}})^2{\displaystyle \frac{\phi \mathrm{\Psi }(2\mathrm{k}_\mathrm{F}/\lambda )}{𝒫_{22}(t)}}\right\}.`$ (40)
Note that the impurity scattering has an influence on the term $`S_0(t)`$ only through the matrix element $`𝒫_{22}(t)`$ in the denominator. If $`\phi =0`$, the above formula corresponds to that obtained in Ref. for pure phonon limited thermoelectric power.

Notice that the pure phonon limited thermoelectric power obtained within the Wilson formalism do not represent any characteristic features of the experimentally observed $`S`$ behavior in simple monovalent metals. Such results for $`S`$ obtained in Ref. were already discussed there in terms of various approximations.

## IV Temperature dependence of the transport coefficients and the Lorenz number.

To compute the transport coefficients as a function of $`t=T/T_D`$ we assume the value of $`2k_\mathrm{F}/\lambda =0.75`$ and $`0\phi 1`$. The temperature dependence of the reduced electrical resistivity following from (26), $`\rho /\rho _{0,ph}`$, which is shown in Fig. 1, and the Seebeck coefficient in Fig. 2 have been computed for $`\phi =0.0,0.2,0.5,1.0,2.0`$ and the corresponding values of $`\mathrm{\Gamma }=\phi \mathrm{\Phi }`$(0.75) = 0.0, 0.0173, 0.0259, 0.0431, 0.0862, 0.173 respectively. As it is seen the impurity scattering slightly lowers the maximum of $`S`$ following from the transfer of the energy between the electron and phonon system. The values of $`\epsilon _s`$ and $`\epsilon _\mathrm{F}`$ have been chosen to be the same as those in Ref., namely $`\epsilon _s=6.0`$ K and $`\epsilon _\mathrm{F}=1.5`$ eV. The electronic thermal conductivity is considerably affected by the impurity scattering, what is seen from the data represented in Fig. 3 and Fig.4. In Fig.3 the reduced thermal conductivity ($`\kappa /\kappa _{0,ph}`$) is shown as a function of $`t`$ in the low temperature range such as in Fig. 4.16 of Ref., where the results of Wilson’s considerations were already illustrated. In Fig. 4 the results are shown in the same temperature range as the thermoelectric power in Fig. 2. We note that he dependence of the thermal conductivity as a function of temperature here obtained by the Ziman variational method is qualitatively the same as that following from Wilson’s considerations. Furthermore, at physically realistic temperatures the values of $`\kappa `$ obtained by the latter method approach a saturation, which is characteristic of monovalent metals. Under the assumption of the same values of the parameters describing the impurity scattering the saturation of $`\kappa `$ following from Wilson formula occurs at a so high temperature that it ceases to be meaningful. According to Ziman, who examined the Wilson formula, physically reasonable results for monovalent metals (saturation and lack of minimum at intermediate temperatures) are obtained when the Umklapp scattering is taken into account. Experimental results for rare earth intermetallic compounds exhibit the existence of a minimum at temperatures such as those seen in Figs. 3 and 4 (see e.g. Fig. 7 in Ref. and references therein), in which the magnetic scattering are also taken into account.

The reduced Lorenz number, $`/`$0, as a function of $`t`$ is shown in Fig. 5 for the same values of the parameters as $`\kappa /\kappa _{0,ph}`$ in Fig. 4. The behavior of this quantity as a function of $`t`$ is qualitatively the same as that following from the Wilson considerations . Note that for only phonon scattering $``$(0) = 0, whereas $`\kappa (0)`$ tends to infinity at zero temperature.

## V Concluding remarks.

Using a simple physical electron model, applying the Ziman variational method within the Boltzmann equation approach and using the same level of approximations for each property we have calculated the phonon-limited electrical resistivity, thermoelectric power and the electronic thermal conductivity of a simple metal and studied how the presence of charged impurities influences these transport coefficients. The method allows us to determine the temperature dependence of the coefficients in a wide temperature interval and to express them in terms of simple and standard functions already useful for examining experimental data. However we are aware that to take into account a more complicated band structure is surely necessary in many cases. In this purpose the Allen method is surely more appropriate though the task needs to bear upon numerical technicalities from the very beginning. Note that the latter method is strictly applicable to metallic systems, when the electron gas is degenerate, while by using the method of this present paper one advantage is that one can easily consider semiconductor or semimetallic systems as well .

A comment is in order on the results of the present paper obtained in the limit of the degenerate electron gas. As concerns the electrical resistivity and the electronic thermal conductivity (or resistivity) the final results are qualitatively the same as those obtained previously in Refs.. In the case of the thermoelectric power however we can obtain a new evidence as a conclusion, i.e. the maximum at intermediate temperatures is caused by the energy transfer between the conduction electrons and phonons and is lowered as a result of the elastic scattering of the electrons on impurities.

The final formal expression for the electronic thermal resistivity reads as a simple expression: this quantity is proportional to the scattering matrix element $`P_{22}`$, much like the electrical resistivity is proportional to $`P_{11}`$. The result is in fact model independent and is a consequence of confining the scattering matrix to four elements (see Appendix A).

The range of applicability of the method we have used here above cannot be finally discussed without referring to papers using more general and sophisticated methods and/or models. In the first place this concerns the papers in which the electron transport was studied within the formalism of the Boltzmann equation. In the second place a relation to the linear response theory  and the quantum transport equation  will be given. However, by using these methods one cannot obtain simple, compact, and useful expressions for the three transport coefficients, moreover being valid in the wide temperature region experimentally studied. Further complications have also to be expected when taking into account the phonon drag , the virtual recoil  or the electron–phonon renormalisation .

Let us start our discussion with a comparison of our model and results with the other ones obtained by the Ziman variational method within the formalism of the Boltzmann equation. As we stressed at the beginning we confined ourselves to a model of the parabolic electron band and the Debye model of the phonon system. This oversimplified model allowed us to gain a coherent and qualitatively correct description of the three transport coefficients: the electrical resistivity, thermoelectric power and the thermal conductivity (resistivity) for a simple and standard model of the scattering. Any generalization of these results to an arbitrary band structure requires numerical studies at an initial stage. A compact formula in this general case of the Ziman variational method has been obtained only for the electrical resistivity among the three coefficients, a formula which has been called ”Ziman’s resistivity formula” . It has been used to compute the electrical resistivity for a realistic Fermi surface.

Again a more exact method is that of Allen though a numerical one. The electrical resistivity is again simplest to compute but the results for the thermal conductivity  and the thermoelectric power  were also obtained by this method. The essence of the method is the separation of the $`𝐤`$-variation during the scattering into two types: (i) an ”angular variation” over the Fermi surface, and (ii) a ”radial” variation with $`\epsilon (k)`$ perpendicular to the Fermi surface describing the inelastic electron scattering. It is obvious from our results for the thermoelectric power  that taking into account inelastic electron scattering, which is equivalent to considering a sufficient number of harmonics describing the radial variation within the Allen formalism, is of major importance for obtaining a correspondence to experimental results if the scattering of the electrons by excitations such as phonons is to be accounted. In Ref. , in which the lowest order radial harmonic was considered and the analysis was in fact restricted to the Mott formula, a poor correspondence to the experimental results for the thermoelectric power was obtained. Inelastic scattering and the radial harmonics are also important to describe properly the thermal conductivity. In Ref.  the radial harmonics were applied to discuss the influence of the electron–electron scattering on the thermal conductivity. According to our knowledge no such considerations were made to analyze the influence of the electron–phonon scattering neither on the thermal conductivity nor the thermoelectric power.

The assumed statistical independence between the impurities as scattering centers restrict our considerations to low impurity concentration. This is consistent with the experimental fact that the Matthiessen rule is valid below a critical residual resistivity  above which the $`T^5`$ low temperature dependence (following, for instance, from the Bloch–Grüneisen dependence of the electrical resistivity) ceases to be valid. One can hardly estimate such a critical concentration without analyzing a specific system and experimental results.

To estimate the magnitude of the transport coefficients out of the reduced values illustrated on each figure in Sec. IV we present the order of magnitude of the relevant material constants in Appendix B. The magnitude of $`\epsilon _s`$ in Table I is the same as in Ref. and corresponds to the magnitude of the sound velocity and the effective electron mass(es) of real materials.

We start our discussion of more sophisticated methods than the Boltzmann equation formalism by noting that in the linear response theory the validity of the Matthiesen rule, which was assumed by us in a generalized version, is related to the fact that the self-energy of the conduction electrons is the same as the sum of the phonon and impurity self-energy . This holds only in the lowest Born approximation. When higher order processes are taken into account, i.e., when interference between the electron-phonon and electron-impurity interaction is to be considered, the Keldysh quantum transport equation formalism  is apparently better.

In Ref. the same model as in the present paper was considered to study the influence of the electron-phonon-impurity interference on the thermoelectric power. A considerable nonlinearity of $`S`$ as a function of temperature was found, the stronger the higher impurity effective charge. The effect can be hardly compared with that studied in the present paper since it has been obtained under an assumption of elasticity for the electron-phonon scattering whereas the assumption of inelasticity of the electron-phonon scattering is essential  for obtaining the maximum of $`S`$ found in the present paper and Ref. 8. Note that as a result of a weak elastic impurity scattering (considered within the Born approximation) the bump in $`S`$ is found to be lowered with the strength of the impurity interaction or the impurity concentration.

The electron-phonon renormalization  leads also to a nonlinearity of $`S`$ as a function of $`T`$. The effect was studied under the assumption of elastic electron-phonon interaction or in the adiabatic approximation. Again there can be no discussion between our results and those in Ref. and  except for the region of very low temperatures, where the effect of elasticity and renormalization are not effective and where $`S`$ is a linear function of $`T`$ with the same slope  as in the pure crystal .

Though the impurity scattering is known to play an important role in the thermal conductivity at least in the low temperature region there is a very limited number of papers devoted to this coefficient aspect. The basic difficulties and problems related to applying the methods of the linear response formalism to treating the electronic thermal conductivity problem in the pure electron-phonon system are described in Ref.. However, such considerations as those in Ref. have not be generalized for a system with impurities. On the other hand the considerations of Refs., devoted to thermoelectric effects for a model of Debye phonons with fixed impurities, have not been used by these authors in an appropriate way to consider the electronic thermal conductivity. Therefore, a complete theory of the electronic thermal conductivity still requires a thorough consideration of the mutual role of the electron-phonon-impurity interference, phonon renormalization and elasticity of the scattering, much the same as on the thermoelectric power. For comparison to data, in not too good metals, the phonon heat contribution should be also taken into account for the thermal conductivity.

A question may arise if our results can be compared to experimental ones in a straightforward, quantitative way. The answer seems that these are the alkali metals, which exhibit essentially spherical Fermi surface to within a few per cent, that should be first of all considered as materials for the comparison. It occurs, however, that the phonon system and the electron–phonon interaction in these metals are too complicated to be well accounted by the applied approximations. It concerns in the first place, (i), the continuous medium approximation used to treat the phonon system and the deformation potential approximation applied to the electron–phonon interaction (see, e.g., Ref.). In the second place, (ii), the Debye approximation is insufficient for the alkali metals. Finally, in the description of the electron scattering we also neglect the Umklapp processes, which occur important even at very low temperatures  in the alkali metals.

The approximations (i) mean that the longitudinal phonons of long wavelength are only considered, whereas the transverse phonons  and those of short wavelength (contributing also to the Umklapp process) have to be taken into account . Due to a strong elastic anisotropy the Debye approximation (ii) is not appropriate even at low temperatures since a constant frequency surface is distorted from the Debye spherical form . Furthermore, the strong influence of the electronic system on the behavior of the phonons cause that the basic symmetry relations between the elastic constants (Cauchy relations) are no longer valid  and, therefore, even the basic results following from the continuous medium approximation of Ref.  may be questioned. All these factors cause that the simple Bloch approach have to be used with a great caution in attempts of the quantitative description of the electrical and thermal transport in the alkali metals.

The most early investigations  of the alkali metals indicated that one can fix such parameters as those of Appendix B to fit the experimental electrical resistivity to the Bloch–Grüneisen function, provided that the temperature is not too low. Thorough analysis  based on the measured phonon spectra of the alkali metals  showed later that the problem is more complicated and the effects mentioned by us above have to be in fact taken into account. Therefore, even in case of these simplest metals the correct quantitative theory based on first principles is in fact impossible and a quantitative analysis have to be based on a cross section for the scattering of the conduction electrons written in terms of the phonon spectrum resulting from neutron scattering data . Precise experimental measurements of the transport coefficients of the alkali metals at low temperatures  support this conjuncture and reveals other physical effects which should be taken into account for a proper quantitative analysis in this temperature region.

As concerns the thermoelectric power our results indicate that other factors than those in case of the electrical resistivity are important. The impurity scattering occurred less essential than expected. Within the assumed model this is the parameter $`\epsilon _s`$ which besides $`\epsilon _\mathrm{F}`$ is solely responsible for the strength of the inelastic scattering of electrons by phonons and controls the magnitude and sign of $`S`$. The obtained temperature dependence of $`S`$ is the same in character as that obtained experimentally  for all the the alkali metals except Li (which exhibits a peculiar behavior  but the Fermi surface of which comes closest to the Brillouin zone boundaries). In search for a quantitative theory of $`S(T)`$ of a specific metal one should also estimate the order of the contribution of the phonon drag , that following from the electron–phonon renormalization  and the electron–phonon–impurity interference. The described above factors which influence the electrical resistivity in the alkali metals may occur of secondary importance.

The effects of the impurity scattering manifest in most pronounced way in the behavior of the thermal conductivity but due to the validity the Wiedemann–Franz law in the limit of low temperatures the effects of the impurity scattering can be easily extracted out of our results at low temperatures for a comparison with experimental ones . As concerns the comparison of the values of appropriate coefficients following from the theory and experimental data for the alkali metals the same problems as in case of the studies of the electrical resistivity may arise. The Umklapp process are expected to be less dominant at low temperatures than in case of the electrical resistivity but the electron–electron interactions may occur essential for the thermal conductivity since both the experimental and theoretical investigations indicate  that electron–electron scattering in the alkali metals impedes heat flow much more effectively than charge flow.

ACKNOWLEDGEMENTS

KD thanks FNRS and KBN for financial aid during part of this work. MA thanks the Wroclaw PAN staff for its always warm welcome during various stays at the Institute for Low Temperature and Structure Research. Thanks also to various European programs, allowing for international exchanges.

APPENDIX A

The transport coefficients considered in the paper follow from the Onsager expressions for the electrical $`𝐉`$ and thermal $`𝐔`$ currents:

$`𝐉=\sigma 𝐄+LT,`$ (41)
$`𝐔=M𝐄+NT,`$ (42)
which in the ”experimental” form are following

$`𝐄=\rho 𝐉+ST,`$ (43)
$`𝐔=\pi 𝐉\kappa T`$ (44)
with $`\pi =\mathrm{S}\mathrm{T}`$ and

$`\rho =1/\sigma ,S=\rho L,\kappa =M\rho LN.`$ (45)
Within the Ziman variational method the coefficients of (41) are

$`\sigma ={\displaystyle \underset{i,j=1}{}}J_iQ_{ij}J_j,\text{ }L={\displaystyle \frac{1}{T}}{\displaystyle \underset{i,j=1}{}}J_iQ_{ij}U_j,`$ (46)
$`M={\displaystyle \underset{i,j=1}{}}U_iQ_{ij}J_j,`$  $`N={\displaystyle \frac{1}{T}}{\displaystyle \underset{i,j=1}{}}U_iQ_{ij}U_j,`$ (47)
where $`J_i`$ and $`U_i`$ ($`i,j=1,2,\mathrm{}`$) are respectively the electron and thermal trial currents defined by (13)-(14) and $`Q_{ij}`$ is the inverse matrix to the scattering matrix $`P_{ij}`$, i.e. $`Q_{ij}=(P^1)_{ij}`$. In the approximation consisting in abbreviating the combinations in (46) to two components ($`i,j=1,2`$) we obtain (7)–(9) from (45). For a degenerate electron gas, i.e. for sufficiently large $`z\epsilon _\mathrm{F}/k_\mathrm{B}T`$, the final expressions for the transport coefficients are (14) – (16). Notice that the thermal resistivity in particular is proportional to $`P_{22}`$ .

APPENDIX B

The functions describing the trial currents, as written below (15)-(16), are

$`L_0(z)`$ $`=`$ $`(3/2)F_{1/2}(z),`$ (48)
$`L_1(z)`$ $`=`$ $`(3/2)zF_{1/2}(z)+(5/2)F_{3/2}(z),`$ (49)
$`L_2(z)`$ $`=`$ $`(3/2)z^2F_{1/2}(z)5zF_{3/2}(z)+(7/2)F_{5/2}(z).`$ (50)
For completeness we also write down their asymptotic forms

$$L_0(z)z^{3/2},\text{ }L_1(z)(\pi ^2/2)z^{1/2},\text{ }L_2(z)(\pi ^2/3)z^{3/2}.$$
(51)
The coefficients of the trial currents are $`J_0`$ = e $`U_0`$ with

$`U_0`$ $`=`$ $`\{\begin{array}{cc}\frac{1}{6\pi ^2}(\frac{2m}{\mathrm{}^2})^{5/2}(\frac{\mathrm{}}{m})^2\hfill & (𝐯𝐚)\hfill \\ \text{ }\hfill & \text{when the factor is}\hfill \\ \frac{1}{6\pi ^2}(\frac{2m}{\mathrm{}^2})^{5/2}(\frac{\mathrm{}}{m})\hfill & (𝐤𝐚)\hfill \end{array}`$ (52)
i.e. the upper case corresponding to the factor $`(𝐯𝐚)`$, and the lower one to $`(𝐤𝐚)`$ in the trial function (6).

The coefficient which determines the dimension and the order of the magnitude of the phonon scattering matrix depends on the effective electron mass, $`m`$, the volume of the primitive cell, $`V`$, its total mass, $`M`$, the sound velocity $`v_s`$, the phonon wave vector cutoff, $`q_D`$, and the deformation potential constant, $`E_1`$. It reads

$`P_0^{(ph)}`$ $`=`$ $`\{\begin{array}{cc}\frac{VE_1^2}{48\pi ^3Mv_s}(\frac{2m}{\mathrm{}^2})^2(\frac{\mathrm{}}{m})^2q_D^5\hfill & (𝐯𝐚)\hfill \\ \text{ }\hfill & \text{when the factor is }\hfill \\ \frac{VE_1^2}{48\pi ^3Mv_s}(\frac{2m}{\mathrm{}^2})^2q_D^5\hfill & (𝐤𝐚)\text{.}\hfill \end{array}`$ (53)
The coefficient $`\rho _{0,ph}=P_0^{(ph)}/(e^2U_0^2\epsilon _{\mathrm{F}}^{}{}_{}{}^{3})`$ in (35) can be represented by

$$\rho _{0,ph}=48\pi (\mu )^2(\frac{m_0}{\mathrm{}^2e^2})(\frac{m_0}{M})VE_1^2\stackrel{~}{\rho }_{0,ph}$$
(54)
where $`m_0/(\mathrm{}^2e^2)=9.11310^3`$\[eV$`^2`$nm-3\],

$$\stackrel{~}{\rho }_{0,ph}=(\frac{q_D}{2k_\mathrm{F}})^6(v_sq_D)^1=(\frac{q_D}{2k_\mathrm{F}})^6\mathrm{}(k_\mathrm{B}T_D)^1,$$
(55)
where $`m_0`$ is the free electron mass and $`\mu =m/m_0`$. For the value of $`T_D=200K`$ assumed for our representative data we have $`\mathrm{}(k_\mathrm{B}T_D)^1=3.43710^2`$$`\mathrm{\Omega }`$ cm. In Table I we show some representative data of $`\stackrel{~}{\rho }_{0,ph}`$ for $`\epsilon _\mathrm{F}=1.5`$ eV, $`T_D=200`$ K, $`\mu =1`$ and the values of $`\epsilon _s`$ given in the table. They correspond to those in Ref. , where numerical relations between $`\epsilon _s`$ and other constants describing the phonon system are presented.

The screened Coulomb potential scattering contribution to the transport is described in terms of the dimensionless functions $`\mathrm{\Phi }`$ and $`\mathrm{\Psi }`$ defined by (4) and (39). The coefficient $`P_0^{(imp)}`$ of the scattering matrix elements is

$`P_0^{(imp)}`$ $`=`$ $`\{\begin{array}{cc}\frac{1}{3\pi \mathrm{}}n_{imp}Z^2e^4(\frac{2m}{\mathrm{}^2})^2(\frac{\mathrm{}}{m})^2\hfill & (𝐯𝐚)\hfill \\ \text{ }\hfill & \text{when the factor is}\hfill \\ \frac{1}{3\pi \mathrm{}}n_{imp}Z^2e^4(\frac{2m}{\mathrm{}^2})^2\hfill & (𝐤𝐚)\text{.}\hfill \end{array}`$ (56)
where $`n_{imp}`$ is the impurity concentration (their number per unit volume). The residual resistivity $`\rho ^{(imp)}=P_{11}^{(imp)}/(e^2U_0^2\epsilon _{\mathrm{F}}^{}{}_{}{}^{3})`$ can be represented by

$$\rho ^{(imp)}=\frac{Z^2n_{imp}}{n_e\mu }\stackrel{~}{\rho }_{imp}\mathrm{\Phi }(2\mathrm{k}_\mathrm{F}/\lambda )$$
(57)
where $`n_e`$ is the number of the conduction electrons per unit volume, with

$$\stackrel{~}{\rho }_{imp}=\frac{12\pi ^2e^2}{m_0v_{F}^{}{}_{}{}^{3}};$$
(58)
$`v_F`$ is the Fermi velocity, and $`2k_\mathrm{F}/\lambda 1`$ as we mentioned in Sec. II. For the data represented in Table I (free electron gas, $`\epsilon _\mathrm{F}=1.5`$ eV) we have $`\stackrel{~}{\rho }_{imp}=0.075\mathrm{\Omega }`$ cm.

In order to relate the magnitude of $`\mathrm{\Gamma }`$ in (25)–(26) with the number of impurities in the sample we represent it as $`\stackrel{~}{\phi }`$

$$\mathrm{\Gamma }=\frac{\rho ^{(\mathrm{i}\mathrm{m}\mathrm{p})}}{\rho _{0,\mathrm{p}\mathrm{h}}}=\frac{\stackrel{~}{\rho }_{\mathrm{i}\mathrm{m}\mathrm{p}}}{\rho _{0,\mathrm{p}\mathrm{h}}}\mathrm{\Phi }(2\mathrm{k}_\mathrm{F}/\lambda )\frac{\mathrm{Z}^2\mathrm{n}_{\mathrm{i}\mathrm{m}\mathrm{p}}}{\mathrm{n}_\mathrm{e}\mu }\stackrel{~}{\phi }\mathrm{\Phi }(2\mathrm{k}_\mathrm{F}/\lambda )\frac{\mathrm{Z}^2\mathrm{n}_{\mathrm{i}\mathrm{m}\mathrm{p}}}{\mathrm{n}_\mathrm{e}\mu }$$
(59)
and shall estimate $`\stackrel{~}{\phi }`$. It means that $`\phi `$ (31) is $`\phi =(Z^2n_{imp}/n_e\mu )\stackrel{~}{\phi }`$. For the mass of the unit cell $`M=10^6m_0`$, its volume $`V=0.1`$ nm3 and $`E_1=(2/3)\epsilon _\mathrm{F}=1`$ eV we have $`\rho _{0,ph}0.1\stackrel{~}{\rho }_{0,ph}`$. This is an underestimated value in many cases, thus we may assume $`\rho _{0,ph}=a\stackrel{~}{\rho }_{0,ph}`$ with $`0.1<a<1`$. For $`\epsilon _\mathrm{F}=1.5`$ eV, $`T_D=200`$ K $`\mu =1`$ the value of $`\stackrel{~}{\rho }_{imp}`$ is: $`\stackrel{~}{\rho }_{imp}0.1\mathrm{\Omega }`$cm. The latter value along with those ones for $`\rho _{0,ph}`$ following from the values of $`\stackrel{~}{\rho }_{0,ph}`$ presented the Table I yields an estimate of $`\stackrel{~}{\phi }`$.

Finally, for information as to the magnitude of the thermal conductivity represented in dimensionless units in the figures we give the magnitude of

$$\stackrel{~}{\kappa }_{0,ph}=\frac{\pi ^2}{3}\frac{_0T_D}{\stackrel{~}{\rho }_{0,ph}}$$
(60)
for the Debye temperature $`T_D=200`$ K in the last column of Table I.

Figure Captions

Figure 1 — Temperature dependence of $`\rho /\rho _{0,ph}`$ resulting from Eq.(26) for values of the parameters $`2k_\mathrm{F}/\lambda =0.75`$ and the relative scattering strength $`\phi =0.0,0.2,0.5,1.0`$. They correspond to the values of $`\mathrm{\Gamma }=\phi \mathrm{\Phi }`$(0.75) which are 0.0, 0.0173, 0.0431, 0.0862, respectively.

Figure 2 — Temperature dependence of $`S/S_{k,e}`$ for values of the parameters as in Fig.1 with $`\epsilon _\mathrm{F}=1.5`$ eV, $`\epsilon _s=6`$ K, and the effective electron mass equal to that of a free electron. $`S_{k,e}`$ = $`k_B/e`$ = 86 $`\mu `$ V/K.

Figure 3 — Temperature dependence of the reduced thermal conductivity below $`T_D`$, for $`2k_\mathrm{F}/\lambda =0.75`$ and $`\phi =0.0,\mathrm{\hspace{0.17em}0.2},\mathrm{\hspace{0.17em}0.5},\mathrm{\hspace{0.17em}1.0},\mathrm{\hspace{0.17em}2.0}`$; the corresponding values of $`\mathrm{\Gamma }`$ are 0.0, 0.0173, 0.0431, 0.0862, 0.173, respectively. For $`\mathrm{\Gamma }`$ = 0, the value of $`\kappa `$ is infinite. Note that for the magnitude of $`\mathrm{\Gamma }`$ as large as 2.0 there is a plateau of $`\kappa `$ instead of the maximum at $`T0.1T_D`$.

Figure 4 — Temperature dependence of the reduced thermal conductivity in the same temperature range as that displayed for the thermoelectric power in Fig.2. The value of $`2k_\mathrm{F}/\lambda `$ is the same as in Fig.3, i.e. 0.75, and $`\phi =0.0,\mathrm{\hspace{0.17em}0.2},\mathrm{\hspace{0.17em}0.5},\mathrm{\hspace{0.17em}1.0},\mathrm{\hspace{0.17em}2.0}`$.

Figure 5 — Temperature dependence of the reduced Lorenz number in the same temperature range as that of the thermoelectric power in Fig.2. The value of $`2k_\mathrm{F}/\lambda `$ is 0.75 as in Fig.3 , and $`\phi =0.0,\mathrm{\hspace{0.17em}0.2},\mathrm{\hspace{0.17em}0.5},\mathrm{\hspace{0.17em}1.0},\mathrm{\hspace{0.17em}2.0}`$.