Fluctuation-dissipation theorems classical model

We compute below the velocity and displacement correlation functions, first, of a classical, then, of a quantal, Brownian particle. In contrast to its velocity, which thermalizes, the displacement x(t) — x(l0) of the particle with respect to its position at a given time never attains equilibrium (whatever the temperature, and even at T = 0). The model allows for a discussion of the corresponding modifications of the fluctuation-dissipation theorem. 

The Kramers model consists of a classical particle of mass m moving on a one-dimensional potential surface V(x) (Fig. 1) under the influence of Markovian random force R(t) and damping y, which are related to each other and to the temperature T by the fluctuation dissipation theorem. 

Here the first two terms just give ma = Force as mass times the second time derivative of the friction equal to the F as the negative derivative of potential, y is the memory friction, and F(t) is the random force. Thus the complex dynamics of all degrees of freedom other than the reaction coordinate are included in a statistical treatment, and the reaction coordinate plus environment are modeled as a modified one-dimensional system. What allows realistic simulation of complex systems is that the statistics of the environment can in fact be calculated from a formal prescription. This prescription is given by the Fluctuation-Dissipation theorem, which yields the relation between the friction and the random force. In particular, this theory shows how to calculate the memory friction from a relatively short-time classical simulation of the reaction coordinate. The Quantum Kramers approach. 

The interatomic interaction potential Pgg on the surface depends only ony. When the primary zone consists of more than one atom, the interaction between them is aharmonic. However, for a one-atom primary zone, the potential is modeled as harmonic with vibrational frequency 0)g. The fluctuation force F(t), acting on the atom, and the dissipation y(t) due to the interactions with the bafli are connected by the classical fluctuation-dissipation theorem, Eq. (23). 

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