ncomms3144模拟伸展的分子中非绝热动态的半经典Monte-Carlo方法 OPEN.pdfVIP

ARTICLE Received 11 Feb 2013 | Accepted 14 Jun 2013 | Published 18 Jul 2013 DOI: 10.1038/ncomms3144 OPEN Semiclassical Monte-Carlo approach for modelling non-adiabatic dynamics in extended molecules Vyacheslav N. Gorshkov1,2, Sergei Tretiak1 Dmitry Mozyrsky1 Modelling of non-adiabatic dynamics in extended molecular systems and solids is a next frontier of atomistic electronic structure theory. The underlying numerical algorithms should operate only with a few quantities (that can be ef?ciently obtained from quantum chemistry), provide a controlled approximation (which can be systematically improved) and capture important phenomena such as branching (multiple products), detailed balance and evolution of electronic coherences. Here we propose a new algorithm based on Monte-Carlo sampling of classical trajectories, which satis?es the above requirements and provides a general framework for existing surface hopping methods for non-adiabatic dynamics simulations. In particular, our algorithm can be viewed as a post-processing technique for analysing numerical results obtained from the conventional surface hopping approaches. Presented numerical tests for several model problems demonstrate ef?ciency and accuracy of the new method. 1 Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. 2 National Technical University of Ukraine, Kiev 03056, Ukraine. Correspondence and requests for materials should be addressed to S.T. (email: tretiak@) or to D.M. (email: mozyrsky@). NATURE COMMUNICATIONS | 4:2144 | DOI: 10.1038/ncomms3144 | /naturecommunications 1 2013 Macmillan Publishers Limited. All rights reserved. ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3144 omputational chemistry became a mature ?eld able to In this paper, we propose a practical computational approach address many problems of chemistry and materials