一种基于新组合的多组态含时哈特里（MCTDH）方法，用于求解具有一般势能面的薛定谔方程。

A new collocation-based multi-configuration time-dependent Hartree (MCTDH) approach for solving the Schrödinger equation with a general potential energy surface.

机构信息

Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada.

出版信息

J Chem Phys. 2018 Jan 28;148(4):044115. doi: 10.1063/1.5018793.

Abstract

We present a new collocation-based multi-configuration time-dependent Hartree (MCTDH) approach for solving the Schrödinger equation required to compute (ro-)vibrational spectra, photodissociation cross sections, reaction rate constants, etc., that can be used with general potential energy surfaces. Collocation obviates the need for quadrature and facilitates using complicated kinetic energy operators. When the basis is good, the accuracy of collocation solutions to the Schrödinger equation is not sensitive to the choice of the collocation points. We test the collocation MCTDH equations we derive by showing that they can be used to compute accurate vibrational energy levels of CH. It is possible to choose (imaginary) time-independent collocation points with which collocation-based MCTDH energies are accurate. It is therefore not necessary to calculate potential values many times during the propagation.

摘要

我们提出了一种新的基于组合的多组态含时 Hartree（MCTDH）方法，用于求解薛定谔方程，以计算（旋转）振动光谱、光解截面、反应速率常数等，该方法可与一般势能面一起使用。配置法避免了需要进行求积和简化复杂动能算子的使用。当基函数较好时，配置法对薛定谔方程的解的准确性对配置点的选择不敏感。我们通过展示它们可以用于计算 CH 的精确振动能级来测试我们推导出的配置 MCTDH 方程。可以选择（虚）时间独立的配置点，使基于配置的 MCTDH 能量非常准确。因此，在传播过程中不需要多次计算势能值。