School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom.
Department of Chemistry and Centre for Scientific Computing, University of Warwick, Coventry CV4 7AL, United Kingdom.
J Chem Phys. 2019 Jan 28;150(4):041101. doi: 10.1063/1.5086358.
The method of direct variational quantum nuclear dynamics in a basis of Gaussian wavepackets, combined with the potential energy surfaces fitted on-the-fly using Gaussian process regression, is described together with its implementation. Enabling exact and efficient analytic evaluation of Hamiltonian matrix elements, this approach allows for black-box quantum dynamics of multidimensional anharmonic molecular systems. Example calculations of intra-molecular proton transfer on the electronic ground state of salicylaldimine are provided, and future algorithmic improvements as well as the potential for multiple-state non-adiabatic dynamics are discussed.
描述了一种基于高斯波包的直接变分量子核动力学方法，该方法结合了使用高斯过程回归实时拟合的势能面，并展示了其实现方法。该方法通过精确且高效的哈密顿矩阵元的解析评估，实现了多维非谐分子体系的黑盒量子动力学。提供了水杨醛亚胺电子基态上分子内质子转移的实例计算，并讨论了未来的算法改进以及多态非绝热动力学的潜力。
