Quasi-direct Quantum Molecular Dynamics: The Time-Dependent Adaptive Density-Guided Approach for Potential Energy Surface Construction.

Abstract

We present a new quasi-direct quantum molecular dynamics computational method which offers a compromise between quantum dynamics using a precomputed potential energy surface (PES) and fully direct quantum dynamics. This method is termed the time-dependent adaptive density-guided approach (TD-ADGA) and is a method for constructing a PES on the fly during a dynamics simulation. This is achieved by acquisition of new single-point (SP) calculations and refitting of the PES, depending on the need of the dynamics. The TD-ADGA is a further development of the adaptive density-guided approach (ADGA) for PES construction where the placement of SPs is guided by the density of the nuclear wave function. In TD-ADGA, the ADGA framework has been integrated into the time propagation of the time-dependent nuclear wave function and we use the reduced one-mode density of this wave function to guide when and where new SPs are placed. The PES is thus extended or updated if the wave function moves into new areas or if a certain area becomes more important. Here, we derive equations for the reduced one-mode density for the time-dependent Hartree (TDH) method and for multiconfiguration time-dependent Hartree (MCTDH) methods, but the TD-ADGA can be used with any time-dependent wave function method as long as a density is available. The TD-ADGA method has been investigated on molecular systems containing single- and double-minimum potentials and on single-mode and multi-mode systems. We explore different approaches to handle the fact that the TD-ADGA involves a PES that changes during the computation and show how results can be obtained that are in very good agreement with results obtained by using an accurate reference PES. Dynamics with TD-ADGA is essentially a black box procedure, where only the initialization of the system and how to compute SPs must be provided. The TD-ADGA thus makes it easier to carry out quantum molecular dynamics and the quasi-direct framework opens up the possibility to compute quantum dynamics accurately for larger molecular systems.