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Springer series in chemical physics

Do We Have a Consistent Non-Adiabatic Quantum-Classical Statistical Mechanics?

Giovanni Ciccotti, S. Caprara, Federica Agostini

Published Jan 1, 2009• 0 citations
Publisher
DOI
10.1007/978-3-642-02306-4_14

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Theoretical description and simulation of large quantum coherent systems out of equilibrium remains a daunting task. Here we are developing a new approach to it based on the Pechukas-Yukawa formalism, which is especially convenient in case of an adiabatically slow external perturbation. In this formalism the dynamics of energy levels in an externally perturbed quantum system as a function of the perturbation parameter is mapped on that of a fictitious one-dimensional classical gas of with cubic repulsion. Equilibrium statistical mechanics of this gas allows to reproduce the random matrix theory of energy levels. In the present work, we develop the nonequilibrium statistical mechanics of the gas, starting with the derivation of the Bogoliubov-Born-Green-Kirkwood-Yvon (BBGKY) chain of equations for the appropriate generalized distribution functions. Sets of approximate kinetic equations can be consistently obtained by breaking this chain at a particular point (i.e. approximating all higher-order distribution functions by the products of the lower-order ones). When complemented by the equations for the level occupation numbers and inter-level transition amplitudes, they allow to describe the nonequilibrium evolution of the quantum state of the system, which can describe better a large quantum coherent system than the currently used approaches. In particular, we find that corrections to the factorized approximation of the distribution function scale as 1/N, where N is the number of the Pechukas gas particles (i.e. energy levels in the system).