화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.112, No.50, 15966-15972, 2008
Semiclassical Nonadiabatic Surface-hopping Wave Function Expansion at Low Energies: Hops in the Forbidden Region
The accuracy of a semiclassical surface-hopping expansion of the time-independent wave function for problems in which the nonadiabatic coupling is peaked in the classically forbidden regions is studied numerically for a one-dimensional curve-crossing problem. This surface-hopping expansion has recently been shown to satisfy the Schrodinger equation to all orders in h and all orders in the nonadiabatic coupling. It has also been found to provide very accurate transition probabilities for problems in which the crossing points of the diabatic energy surfaces are classically allowed. In the numerical study reported here, transition probabilities are evaluated for energies well below the crossing point energy. It is found that the expansion provides accurate results for transition probabilities as small as 10(-11).