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J Chem Phys. 2014 May 21;140(19):194107. doi: 10.1063/1.4875702.

Coherence penalty functional: a simple method for adding decoherence in Ehrenfest dynamics.

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  • 1Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
  • 2School of Physics, Complex and Adaptive Systems Laboratory, University College Dublin, Dublin 4, Ireland.


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.

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