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arXiv · 1611.06525

Mixed quantum-classical dynamics using collective electronic variables: A better alternative to electronic friction theories

Ilya G. Ryabinkin·Artur F. Izmaylov
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Abstract

An accurate description of nonadiabatic dynamics of molecular species on metallic surfaces poses a serious computational challenge associated with a multitude of closely-spaced electronic states. We propose a mixed quantum-classical scheme that addresses this challenge by introducing collective electronic variables. These variables are defined through analytic block-diagonalization applied to the time-dependent Hamiltonian matrix governing the electronic dynamics. We compare our scheme with the Ehrenfest approach and with a full-memory electronic friction model on a one-dimensional "adatom + atomic chain" model. Our simulations demonstrate that collective-mode dynamics with only few (2-3) electronic variables is robust and can describe a variety of situations: from a chemisorbed atom on an insulator to an atom on a metallic surface. Our molecular model also reveals that the friction approach is prone to unpredictable and catastrophic failures.

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Ilya G. Ryabinkin, Artur F. Izmaylov. 2016-11-20. Mixed quantum-classical dynamics using collective electronic variables: A better alternative to electronic friction theories. https://doi.org/10.1021/acs.jpclett.6b02712

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