Generalized Langevin equation for solids. I. Rigorous derivation and main properties

Abstract

We demonstrate explicitly that the derivation by Adelman and Doll (AD) [J. Chem. Phys. 64, 2375 (1976)] of the generalized Langevin equation (GLE) to describe dynamics of an extended solid system by considering its finite subsystem is inconsistent because it relies on performing statistical averages over the entire system when establishing properties of the random force. This results in the random force representing a nonstationary process opposite to one of the main assumptions made in AD that the random force corresponds to a stationary stochastic process. This invalidates the derivation of the Brownian (or Langevin) form of the GLE in AD. Here we present a different and more general approach in deriving the GLE. Our method generalizes that of AD in two main aspects: (i) the structure of the finite region can be arbitrary (e.g., anharmonic), and (ii) ways are indicated in which the method can be implemented exactly if the phonon Green's function of the harmonic environment region surrounding the anharmonic region is known, which is, e.g., the case when the environment region represents a part of a periodic solid (the bulk or a surface). We also show that in general after the local perturbation has ceased, the system returns to thermodynamic equilibrium with the distribution function for region 1 being canonical with respect to an effective interaction between atoms, which includes instantaneous response of the surrounding region. Note that our method does not rely on the assumption made in AD that the stochastic force correlation function depends on the times difference only (i.e., the random force corresponds to a stationary random process). In fact, we demonstrate explicitly that generally this is not the case. Still, the correct GLE can be obtained, which satisfies exactly the fluctuation-dissipation theorem.