Markovian diabatic dynamics near a continuum

PHYS 440

Neil Shenvi1, Hongzhi Cheng2, and John C. Tully, john.tully@yale.edu1. (1) Department of Chemistry, Yale University, New Haven, CT 06520-8107, (2) Department of Physics, Yale University, New Haven, CT 06520-8107
When an electron in a localized orbital approaches a continuum, resonant charge transfer can occur. If the continuum has a large band width, the charge transfer will be Markovian in character. In this paper, we introduce a simple method for simulating the quantum dynamics of such a system by decoupling the equations of motions for the ionic and neutral diabats. We compare our method to both exact quantum dynamics and Ehrenfest dynamics. Numerical results show that our diabatic dynamics method accurately describes the quantum nuclear dynamics near a wide-band continuum. Our method successfully predicts non-trivial quantum mechanical effects such as partial reflection which cannot be captured by more traditional methods.
 

Poster Session
7:30 PM-10:00 PM, Wednesday, 13 September 2006 Moscone Center -- Hall D, Poster

Division of Physical Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006