Akimov Alexey V
Department of Chemistry , University at Buffalo, The State University of New York , Buffalo , New York 14260 , United States.
J Phys Chem Lett. 2018 Oct 18;9(20):6096-6102. doi: 10.1021/acs.jpclett.8b02826. Epub 2018 Oct 8.
The outcomes of nonadiabatic molecular dynamics (NA-MD) calculations are modulated by the parameters entering the time-dependent Schrödinger equation (TD-SE). The adiabatic states are commonly used as the basis in which the TD-SE is integrated. However, the phase inconsistencies of such states along the nuclear trajectories obtained in NA-MD simulations may render the wave function and other relevant properties ill-behaving, adversely affecting the dynamics. This work illustrates the consequence of adiabatic state phase inconsistencies in nonadiabatic Ehrenfest dynamics. A simple phase-correction approach is proposed and is demonstrated to alter the dynamics to make it consistent with the reference calculations done in the phase-consistent diabatic representation.
非绝热分子动力学（NA-MD）计算的结果受到进入含时薛定谔方程（TD-SE）的参数的调制。绝热态通常被用作积分TD-SE的基。然而，在NA-MD模拟中沿着核轨迹获得的这些态的相位不一致可能会使波函数和其他相关性质表现不佳，对动力学产生不利影响。这项工作说明了非绝热埃伦费斯特动力学中绝热态相位不一致的后果。提出了一种简单的相位校正方法，并证明该方法可以改变动力学，使其与在相位一致的 diabatic 表象中进行的参考计算相一致。
