Noyes Laboratories, California Institute of Technology, 127-72, Pasadena, California 91125, USA.
J Chem Phys. 2010 Jun 14;132(22):224304. doi: 10.1063/1.3430508.
A classical theory is proposed to describe the non-RRKM effects in activated asymmetric top triatomic molecules observed numerically in classical molecular dynamics simulations of ozone. The Coriolis coupling is shown to result in an effective diffusive energy exchange between the rotational and vibrational degrees of freedom. A stochastic differential equation is obtained for the K-component of the rotational angular momentum that governs the diffusion.
提出了一个经典理论来描述在经典分子动力学模拟臭氧中观察到的激活不对称三体分子中的非 RRKM 效应。结果表明,科里奥利耦合导致了旋转和振动自由度之间有效的扩散能量交换。得到了一个控制扩散的 K 分量的旋转角动量的随机微分方程。