Chemistry Department, Wehr Chemistry Building, Marquette University, Milwaukee, Wisconsin 53201-1881, USA.
J Chem Phys. 2011 Apr 14;134(14):144107. doi: 10.1063/1.3576103.
A mixed quantum-classical approach to the description of collisional energy transfer is proposed in which the vibrational motion of an energized molecule is treated quantum mechanically using wave packets, while the collisional motion of the molecule and quencher and the rotational motion of the molecule are treated using classical trajectories. This accounts rigorously for quantization of vibrational states, zero-point energy, scattering resonances, and permutation symmetry of identical atoms, while advantage is taken of the classical scattering regime. Energy is exchanged between vibrational, rotational, and translational degrees of freedom while the total energy is conserved. Application of this method to stabilization of the van der Waals states in ozone is presented. Examples of mixed quantum-classical trajectories are discussed, including an interesting example of supercollision. When combined with an efficient grid mapping procedure and the reduced dimensionality approximation, the method becomes very affordable computationally.
提出了一种混合量子经典方法来描述碰撞能量转移，其中使用波包对激发分子的振动运动进行量子力学处理，而分子和猝灭剂的碰撞运动以及分子的旋转运动则使用经典轨迹进行处理。这严格考虑了振动状态的量子化、零点能、散射共振以及相同原子的排列对称性，同时利用了经典散射状态。在总能量守恒的情况下，振动、旋转和平移自由度之间进行能量交换。本文介绍了将该方法应用于臭氧范德华态稳定化的情况。讨论了混合量子经典轨迹的示例，包括一个有趣的超碰撞示例。当与高效的网格映射过程和降维近似相结合时，该方法在计算上变得非常经济实惠。
