Berlin 2014 – scientific programme

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MO: Fachverband Molekülphysik

MO 4: Theory 1: Molecular Dynamics

MO 4.2: Talk

Monday, March 17, 2014, 14:30–14:45, BEBEL SR144

A ring-polymer approach to electronically nonadiabatic dynamics within the mapping representation — •Jeremy O. Richardson and Michael Thoss — Institut für Theoretische Physik und Interdisziplinäres Zentrum für Molekulare Materialien, Friedrich-Alexander-Universität Erlangen-Nürnberg

A new method [1] based on an extension of ring-polymer molecular dynamics is proposed for the calculation of thermal correlation functions in electronically nonadiabatic systems for which the Born-Oppenheimer approximation is not valid. The ring-polymer dynamics are performed using a continuous-variable representation of the electronic states within the mapping approach, such that the electronic and nuclear degrees of freedom are treated on an equal footing. Illustrative applications of the method to models for nonadiabatic processes with two electronic states coupled strongly to a nuclear mode show good agreement with exact quantum results for the dynamics over short to moderate times and reveal a systematic improvement over the classical implementation of the mapping approach (single-bead limit). Being based on trajectories, the method scales well with the number of degrees of freedom and will be applicable to simulate certain nonadiabatic processes in complex molecular systems.

[1] J. O. Richardson and M. Thoss. J. Chem. Phys. 139, 031102 (2013).