期刊
MOLECULAR PHYSICS
卷 108, 期 11, 页码 1471-1479出版社
TAYLOR & FRANCIS LTD
DOI: 10.1080/00268971003720314
关键词
computer simulation; nonadiabatic dynamics; mean-field; surface-hopping; conical intersection; Born-Oppenheimer
The mean-field and surface-hopping approaches are mixed quantum-classical algorithms designed to efficiently incorporate nonadiabatic effects into molecular dynamics simulations. In this report, analytical relations underpinning the two methods are derived within the adiabatic basis to provide an implementation-level overview, with particular attention given to two avoidable sources of energy conservation deviation. It is not widely known that accuracy improvements can be obtained at negligible computational expense by allowing: (a) construction of the Schrodinger equation to account for analytic electronic phase propagation, and (b) inclusion of a Hellman-Feynman correctional term in the calculation of atomic forces. Particular emphasis on the algebraic formalism contrasts these inherent approximations, vis-a-vis the correctional approaches. The sensitivity of energy conservation with respect to phase propagation is exemplified by simulation of Xe-3(+) molecular photodissociation on the repulsive Pi(1/2)(u) excited surface. Simulations of a representative two-state avoided crossing system are presented to exemplify analytic quantities of the mean-field and surface-hopping approaches as well as to illustrate the inclusion of the Hellman-Feynman correctional term. Nonadiabatic propagation of the molecular wavefunction is observed by monitoring ground and excited state occupational probabilities, energy conservation, and nonadiabatic coupling as the system evolves along the model potential energy surfaces.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据