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Nonadiabatic dynamics of electrons and atoms under nonequilibrium conditions

Research output: Contribution to journalArticle

Original languageEnglish
Article number014307
Pages (from-to)1-23
JournalPhysical Review B
Volume98
Issue number014307
Early online date23 Jul 2018
DOIs
Accepted/In press3 Jul 2018
E-pub ahead of print23 Jul 2018
PublishedJul 2018

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30 pages, 1 fugure

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Abstract

An approach to nonadiabatic dynamics of atoms in molecular and condensed matter systems under general nonequilibrium conditions is proposed. In this method interaction between nuclei and electrons is considered explicitly up to the second order in atomic displacements defined with respect to the mean atomic trajectory, enabling one to consider movement of atoms beyond their simple vibrations. Both electrons and nuclei are treated fully quantum-mechanically using a combination of path integrals applied to nuclei and nonequilibrium Green's functions to electrons. Our method is partitionless: initially, the entire system is coupled and assumed to be at thermal equilibrium. Then, the exact application of the Hubbard-Stratonovich transformation in mixed real and imaginary times enables us to obtain, without doing any additional approximations, an exact expression for the reduced density matrix for nuclei and hence an effective quantum Liouville equation for them, both containing Gaussian noises. It is shown that the time evolution of the expectation values for atomic positions is described by an infinite hierarchy of stochastic differential equations for atomic positions and momenta and their various fluctuations. The actual dynamics is obtained by sampling all stochastic trajectories. It is expected that applications of the method may include photoinduced chemical reactions (e.g., dissociation), electromigration, and atomic manipulation in scanning tunneling microscopy, to name just a few.

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