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Physical Review

Mobility of Slow Electrons in a Polar Crystal

Richard P. Feynman, R. W. Hellwarth, C. K. Iddings, P. M. Platzman

Published Aug 15, 1962• 401 citations
Publisher

Abstract

We have obtained an approximate expression for the impedance function at all frequencies, temperatures, and coupling strengths of an electron coupled to a polar lattice (a system commonly called a polaron). The starting point for the calculation is the quantum mechanical expression for the expected current. The phonon coordinates are eliminated from this expression by well-known field-theory techniques. The resulting exact "influence functional" is then approximated by a corresponding quadratic "influence functional" which, it is hoped, imitates the real polaron. Correction terms are computed to account for the difference between the approximate impedance and the exact polaron impedance in a manner closely analogous to Feynman's treatment of the polaron self-energy. In fact, the analytic evaluation of the expression for the impedance obtained here is carried out using the approximate "influence functional" that was successfully employed in minimizing the binding (and free) energy of the polaron in earlier calculations. However, the accuracy obtained using this approximation, for the impedance calculation, is less satisfactory and its limitations are discussed. Nevertheless, beginning at intermediate coupling strengths, the approximate impedance produces a level structure of increasing complexity and narrowing resonances as the coupling strengthens. This suggests that further refinements may be fruitful. Methods for finding a better quadratic influence functional for use in our impedance expression as well as ways of improving the expression further are suggested. A comparison of our results with those of the Boltzmann equation points up interesting differences which arise from reversing the order of taking limits of zero frequency and coupling.

DOI
10.1103/physrev.127.1004

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Theory of Polaron Mobility

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The polaron mobility is calculated by making use of the general theory of electrical conductivity. We take the states determined by Feynman's trial action as the unperturbed states and treat the difference between the true action and the trial action as a perturbation. Numerical values of the polaron mobility at very .low temperatures are given and are dis· cussed in comparison with the results obtained by Shultz and .by Morita. § I. Introduction We have investigated the static properties of polaron at finite temperatures in the previous paper1> (hereafter referred to as I). We shall investigB;te the polaron mobility in the present paper. In the same way as in I, we calculate the polaron mobility by using Feynman's path-integral method. In the polaron problem, the interaction between an electron and lattice vibrations is so large that the usual perturbation theoretic treatment fails. Therefore the calculation of the mobility in the present paper will be based on the general theory of electrical conductivity recently developed by many authors,2 > which is applicable to a system which does not allow us to set up the Boltzmann equation. We take the states determined by Feynman's trial action as unperturbed states and treat the difference between the trial action and the true action as a perturba­ tion which yields a decay of electronic current correlation. The following assumptions will be made in the present paper. i) The electrical conductivity is determined by the asymptotic form of a correlation function of electronic current. ii) This asymptotic form has the property of exponential decay in time. These assumptions are valid in the case of weak interaction. It is not sure whether or not they are applicable to the present problem which includes the case of strong interaction. In the present treat­ ment, however, ~he states determined by Feynman's trial action instead of the states of a free electron are chosen as the unperturbed states. It is expected that the perturbation in the former case may be made weaker than in the latter case and that the above mentioned assumptions may be valid. In fact the self­ energy of polaron at 0°K calculated by using these assumptions agrees with that obtained by Feynman3> as will be shown _in § 3. Therefore, the approxi

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The optical absorption of polarons at rest at zero temperature is calculated starting from the Feynman-Hellwarth-Iddings-Platzman (FHIP) theory of the impedance. The results are compared with the results of theories whose physical interpretation is clearer [weak-coupling theory of Gurevich, Lang, and Firsov (GLF) and product-ansatz strong-coupling theory of Kartheuser, Evrard, and Devreese (KED)] in order to obtain a better understanding of the FHIP approximation. We are particularly interested in the possible role of lattice relaxation [leading to relaxed excited states (RES)] in the optical absorption process. If the FHIP perturbation method were used to expand the conductivity (this would be the normal procedure), essentially Franck-Condon transitions would be found in the spectrum, and lattice relaxation would be absent. In this case the results do not fit with the product ansatz and provide merely the asymptotic limit $\ensuremath{\alpha}\ensuremath{\rightarrow}0$, where $\ensuremath{\alpha}$ is the electron-phonon coupling constant. If, however, the impedance function rather than the conductivity is expanded (as preferred by FHIP for intuitive reasons, without further justification) more reliable results for the optical absorption appear. For $\ensuremath{\alpha}>5$, intense absorption peaks now occur, which presumably correspond to transitions to RES, and the results are in qualitative agreement with the predictions of the product-ansatz treatment in this coupling region. Also in the limit $\ensuremath{\alpha}\ensuremath{\rightarrow}0$ the correct behavior is found. For $3\ensuremath{\lesssim}\ensuremath{\alpha}\ensuremath{\lesssim}5$, the interpretation of the results is somewhat delicate but the possibility that RES contribute to the oscillator strength as soon as $\ensuremath{\alpha}>3$ should be considered. The results so obtained for the optical absorption seem reliable at all $\ensuremath{\alpha}$. This provides an indirect justification for the expansion of $Z(\ensuremath{\Omega})$ rather than $\frac{1}{Z(\ensuremath{\Omega})}$ in FHIP theory and a confirmation of the qualitative strong-coupling predictions of KED. The present study indicates that optical absorption peaks due to free polarons should be observable experimentally in crystals for which $\ensuremath{\alpha}>1$.

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Polaron Mobility at Finite Temperature

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The Kadanoff-Baym transport theory leads to an expression for polaron mobility which becomes exact for low, but finite, temperature, ${e}^{\frac{\ensuremath{\Theta}}{T}}\ensuremath{\gg}1$, but not necessarily $\frac{\ensuremath{\Theta}}{T}\ensuremath{\gg}1$. This expression is evaluated exactly in the weak-coupling limit. Comparison with previous variational calculations shows that the latter have not predicted even qualitatively valid corrections to the known asymptotic zero-temperature result. Simple arguments allow the present weak-coupling expression to be extended to finite coupling. These arguments are verified by a quantitative calculation using the Feynman model. It is found that the corrections due to finite temperature are at least as important as those due to a finite coupling constant.

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Kinetic Equations in Polaron Theory

N. N. Bogolubov Jr.

This chapter generalizes works by N.N. Bogolubov and N.N. Bogolubov, Jr. [1,6], and \nis written with the aim of formulating methods of investigation of the electron-phonon \nsystem and the elimination of phonon operators from the corresponding kinetic equations. In particular, a kinetic equation is derived for the interaction of an electron \nwith a phonon field. Moreover, under the proper approximation, the exact Boltzmann equation for the polaron system follows from this kinetic equation. Methods of \ncalculation of the response functions (impedance and admittance), based on the "approximating" Hamiltonian with linear interaction, are also proposed. The equilibrium \ndensity probability function of the particle is also calculated.

CRC Press eBooks•May 17, 2000•0 citations
We have obtained an approximate expression for the impedance function at all frequencies, temperatures, and coupling strengths of an electron coupled to a polar lattice (a system commonly called a polaron). The starting point for the calculation is the quantum mechanical expression for the expected current. The phonon coordinates are eliminated from this expression by well-known field-theory techniques. The resulting exact "influence functional" is then approximated by a corresponding quadratic "influence functional" which, it is hoped, imitates the real polaron. Correction terms are computed to account for the difference between the approximate impedance and the exact polaron impedance in a manner closely analogous to Feynman's treatment of the polaron self-energy. In fact, the analytic evaluation of the expression for the impedance obtained here is carried out using the approximate "influence functional" that was successfully employed in minimizing the binding (and free) energy of the polaron in earlier calculations. However, the accuracy obtained using this approximation, for the impedance calculation, is less satisfactory and its limitations are discussed. Nevertheless, beginning at intermediate coupling strengths, the approximate impedance produces a level structure of increasing complexity and narrowing resonances as the coupling strengthens. This suggests that further refinements may be fruitful. Methods for finding a better quadratic influence functional for use in our impedance expression as well as ways of improving the expression further are suggested. A comparison of our results with those of the Boltzmann equation points up interesting differences which arise from reversing the order of taking limits of zero frequency and coupling.
We develop and compare several analytical approximations for the ground state and zero-temperature polaron dispersion in finite-width, nonparabolic conduction bands. The main focus of the work is an extension of the Feynman variational method to a tight-binding lattice, where the effective-mass approximation is no longer applicable. The resulting variational formulation is not restricted to a specific phonon dispersion or electron-phonon interaction and provides a uniform description across weak-, intermediate-, and strong-coupling regimes. In addition, we revisit and generalize other analytical approaches traditionally formulated for continuum polarons, including canonical transformations and self-consistent Wigner-Brillouin-type approximations. For lattice polarons, these methods exhibit qualitative features absent in the continuum case, such as a nontrivial connection between weak- and strong-coupling limits. We show that an improved Wigner-Brillouin scheme yields a momentum-dependent polaron self-energy free of resonances and in good agreement with numerically exact results. All methods are applied to the Holstein model on a tight-binding lattice and are benchmarked against numerically exact calculations, including diagrammatic Monte Carlo (both our calculations and preceding works) and exact diagonalization results. Furthermore, the analytical approaches are extended to polarons with Rashba-type spin-orbit coupling, providing a stringent test of their applicability in systems with nontrivial band structure. Our results demonstrate that the modified Feynman variational method yields ground-state energies and dispersions with accuracy comparable to, and in many cases exceeding, that of other established analytical approaches. The developed framework offers a versatile and reliable analytical description of lattice polarons beyond the continuum approximation.
The polaron mobility is calculated by making use of the general theory of electrical conductivity. We take the states determined by Feynman's trial action as the unperturbed states and treat the difference between the true action and the trial action as a perturbation. Numerical values of the polaron mobility at very .low temperatures are given and are dis· cussed in comparison with the results obtained by Shultz and .by Morita. § I. Introduction We have investigated the static properties of polaron at finite temperatures in the previous paper1> (hereafter referred to as I). We shall investigB;te the polaron mobility in the present paper. In the same way as in I, we calculate the polaron mobility by using Feynman's path-integral method. In the polaron problem, the interaction between an electron and lattice vibrations is so large that the usual perturbation theoretic treatment fails. Therefore the calculation of the mobility in the present paper will be based on the general theory of electrical conductivity recently developed by many authors,2 > which is applicable to a system which does not allow us to set up the Boltzmann equation. We take the states determined by Feynman's trial action as unperturbed states and treat the difference between the trial action and the true action as a perturba­ tion which yields a decay of electronic current correlation. The following assumptions will be made in the present paper. i) The electrical conductivity is determined by the asymptotic form of a correlation function of electronic current. ii) This asymptotic form has the property of exponential decay in time. These assumptions are valid in the case of weak interaction. It is not sure whether or not they are applicable to the present problem which includes the case of strong interaction. In the present treat­ ment, however, ~he states determined by Feynman's trial action instead of the states of a free electron are chosen as the unperturbed states. It is expected that the perturbation in the former case may be made weaker than in the latter case and that the above mentioned assumptions may be valid. In fact the self­ energy of polaron at 0°K calculated by using these assumptions agrees with that obtained by Feynman3> as will be shown _in § 3. Therefore, the approxi
The optical absorption of polarons at rest at zero temperature is calculated starting from the Feynman-Hellwarth-Iddings-Platzman (FHIP) theory of the impedance. The results are compared with the results of theories whose physical interpretation is clearer [weak-coupling theory of Gurevich, Lang, and Firsov (GLF) and product-ansatz strong-coupling theory of Kartheuser, Evrard, and Devreese (KED)] in order to obtain a better understanding of the FHIP approximation. We are particularly interested in the possible role of lattice relaxation [leading to relaxed excited states (RES)] in the optical absorption process. If the FHIP perturbation method were used to expand the conductivity (this would be the normal procedure), essentially Franck-Condon transitions would be found in the spectrum, and lattice relaxation would be absent. In this case the results do not fit with the product ansatz and provide merely the asymptotic limit $\ensuremath{\alpha}\ensuremath{\rightarrow}0$, where $\ensuremath{\alpha}$ is the electron-phonon coupling constant. If, however, the impedance function rather than the conductivity is expanded (as preferred by FHIP for intuitive reasons, without further justification) more reliable results for the optical absorption appear. For $\ensuremath{\alpha}>5$, intense absorption peaks now occur, which presumably correspond to transitions to RES, and the results are in qualitative agreement with the predictions of the product-ansatz treatment in this coupling region. Also in the limit $\ensuremath{\alpha}\ensuremath{\rightarrow}0$ the correct behavior is found. For $3\ensuremath{\lesssim}\ensuremath{\alpha}\ensuremath{\lesssim}5$, the interpretation of the results is somewhat delicate but the possibility that RES contribute to the oscillator strength as soon as $\ensuremath{\alpha}>3$ should be considered. The results so obtained for the optical absorption seem reliable at all $\ensuremath{\alpha}$. This provides an indirect justification for the expansion of $Z(\ensuremath{\Omega})$ rather than $\frac{1}{Z(\ensuremath{\Omega})}$ in FHIP theory and a confirmation of the qualitative strong-coupling predictions of KED. The present study indicates that optical absorption peaks due to free polarons should be observable experimentally in crystals for which $\ensuremath{\alpha}>1$.
The phonon spectral function of the one-dimensional Holstein model is obtained within weak and strong-coupling approximations based on analytical self-energy calculations. The characteristic excitations found in the limit of small charge-carrier density are related to the known (electronic) spectral properties of Holstein polarons such as the polaron band dispersion. Particular emphasis is laid on the different physics occurring in the adiabatic and anti-adiabatic regimes, respectively. Comparison is made with a cluster approach exploiting exact numerical results on small systems to yield an approximation for the thermodynamic limit. This method, similar to cluster perturbation theory, confirms the analytical findings, and yields accurate results also in the intermediate-coupling regime.
The Kadanoff-Baym transport theory leads to an expression for polaron mobility which becomes exact for low, but finite, temperature, ${e}^{\frac{\ensuremath{\Theta}}{T}}\ensuremath{\gg}1$, but not necessarily $\frac{\ensuremath{\Theta}}{T}\ensuremath{\gg}1$. This expression is evaluated exactly in the weak-coupling limit. Comparison with previous variational calculations shows that the latter have not predicted even qualitatively valid corrections to the known asymptotic zero-temperature result. Simple arguments allow the present weak-coupling expression to be extended to finite coupling. These arguments are verified by a quantitative calculation using the Feynman model. It is found that the corrections due to finite temperature are at least as important as those due to a finite coupling constant.
This chapter generalizes works by N.N. Bogolubov and N.N. Bogolubov, Jr. [1,6], and \nis written with the aim of formulating methods of investigation of the electron-phonon \nsystem and the elimination of phonon operators from the corresponding kinetic equations. In particular, a kinetic equation is derived for the interaction of an electron \nwith a phonon field. Moreover, under the proper approximation, the exact Boltzmann equation for the polaron system follows from this kinetic equation. Methods of \ncalculation of the response functions (impedance and admittance), based on the "approximating" Hamiltonian with linear interaction, are also proposed. The equilibrium \ndensity probability function of the particle is also calculated.