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Title: Coherence penalty functional: A simple method for adding decoherence in Ehrenfest dynamics

We present a new semiclassical approach for description of decoherence in electronically non-adiabatic molecular dynamics. The method is formulated on the grounds of the Ehrenfest dynamics and the Meyer-Miller-Thoss-Stock mapping of the time-dependent Schrödinger equation onto a fully classical Hamiltonian representation. We introduce a coherence penalty functional (CPF) that accounts for decoherence effects by randomizing the wavefunction phase and penalizing development of coherences in regions of strong non-adiabatic coupling. The performance of the method is demonstrated with several model and realistic systems. Compared to other semiclassical methods tested, the CPF method eliminates artificial interference and improves agreement with the fully quantum calculations on the models. When applied to study electron transfer dynamics in the nanoscale systems, the method shows an improved accuracy of the predicted time scales. The simplicity and high computational efficiency of the CPF approach make it a perfect practical candidate for applications in realistic systems.
Authors:
 [1] ;  [2] ;  [3] ;  [1]
  1. Department of Chemistry, University of Rochester, Rochester, New York 14627 (United States)
  2. (United States)
  3. School of Physics, Complex and Adaptive Systems Laboratory, University College Dublin, Dublin 4 (Ireland)
Publication Date:
OSTI Identifier:
22304422
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 19; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; ACCURACY; EFFICIENCY; ELECTRON TRANSFER; HAMILTONIANS; MOLECULAR DYNAMICS METHOD; NANOSTRUCTURES; SCHROEDINGER EQUATION; SEMICLASSICAL APPROXIMATION; TIME DEPENDENCE; WAVE FUNCTIONS