Coffey William T, Kalmykov Yuri P, Titov Sergey V
Department of Electronic and Electrical Engineering, Trinity College, Dublin 2, Ireland.
J Chem Phys. 2004 May 15;120(19):9199-211. doi: 10.1063/1.1703525.
The extension of the Kramers theory of the escape rate of a Brownian particle from a potential well to the entire range of damping proposed by Mel'nikov and Meshkov [J. Chem, Phys. 85, 1018 (1986)] is applied to the rotational Brownian motion of fixed axis rotators in a double well cosine potential. The procedure yields an expression for the Kramers escape rate valid for all values of the dissipation including the very low damping (VLD), very high damping (VHD), and crossover regimes. This equation provides a good asymptotic estimate of the correlation time tau per pendicular of the longitudinal dipole moment correlation function calculated by solving the underlying Langevin equation using the matrix-continued fraction method. Moreover, for low barriers, where the Mel'nikov and Meshkov approach is not applicable, analytic equations for tau in the VLD and VHD limits are derived and a simple extrapolating equation that is valid for all values of the damping is proposed.
梅尔尼科夫和梅什科夫[《化学物理杂志》85, 1018 (1986)]将克拉默斯关于布朗粒子从势阱逸出速率的理论扩展到整个阻尼范围,该理论被应用于双阱余弦势中固定轴转子的旋转布朗运动。此过程得出了一个适用于所有耗散值的克拉默斯逸出速率表达式,包括极低阻尼(VLD)、极高阻尼(VHD)以及交叉区域。该方程对通过矩阵连分数法求解基础朗之万方程计算得到的纵向偶极矩相关函数的相关时间τ⊥给出了良好的渐近估计。此外,对于梅尔尼科夫和梅什科夫方法不适用的低势垒情况,推导了VLD和VHD极限下τ的解析方程,并提出了一个适用于所有阻尼值的简单外推方程。