Molecular dynamics with electronic transitions

来自掌桥科研

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319

作者：

Tully，C John

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摘要：

A method is proposed for carrying out molecular dynamics simulations of processes that involve electronic transitions. The time dependent electronic Schrdinger equation is solved self‐consistently with the classical mechanical equations of motion of the atoms. At each integration time step a decision is made whether to switch electronic states, according to probabilistic ''fewest switches'' algorithm. If a switch occurs, the component of velocity in the direction of the nonadiabatic coupling vector is adjusted to conserve energy. The procedure allows electronic transitions to occur anywhere among any number of coupled states, governed by the quantum mechanical probabilities. The method is tested against accurate quantal calculations for three one‐dimensional, two‐state models, two of which have been specifically designed to challenge any such mixed classical–quantal dynamical theory. Although there are some discrepancies, initial indications are encouraging. The model should be applicable to a wide variety of gas‐phase and condensed‐phase phenomena occurring even down to thermal energies.

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关键词：

Theoretical or Mathematical/ digital simulation molecular dynamics method/ fewest switches algorithm one dimensional two state model electronic transitions molecular dynamics simulations time dependent electronic Schrodinger equation classical mechanical equations of motion integration time step nonadiabatic coupling vector coupled states quantum mechanical probabilities gas-phase condensed-phase phenomena thermal energies/ A6120J Computer simulation of static and dynamic liquid behaviour