Numerical Implementation and Test of the Modified Variational Multiconfigurational Gaussian Method for High-Dimensional Quantum Dynamics

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-08, Vol.117 (32), p.6948-6959
• Main Authors: Ronto, Miklos, Shalashilin, Dmitrii V
• Format: Article
• Language: English
• Subjects: Atomic and molecular physics; Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations); Coherence; Derivatives; Electronic structure of atoms, molecules and their ions: theory; Exact sciences and technology; Gaussian; Inversions; Mathematical analysis; Mathematical models; Physics; Trajectories; Wave functions
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp310976d

In this paper, a new numerical implementation and a test of the modified variational multiconfigurational Gaussian (vMCG) equations are presented. In vMCG, the wave function is represented as a superposition of trajectory guided Gaussian coherent states, and the time derivatives of the wave function parameters are found from a system of linear equations, which in turn follows from the variational principle applied simultaneously to all wave function parameters. In the original formulation of vMCG, the corresponding matrix was not well-behaved and needed regularization, which required matrix inversion. The new implementation of the modified vMCG equations seems to have improved the method, which now enables straightforward solution of the linear system without matrix inversion, thus achieving greater efficiency, stability and robustness. Here the new version of the vMCG approach is tested against a number of benchmarks, which previously have been studied by split-operator, multiconfigurational time-dependent Hartree (MCTDH) and multilayer MCTDH (ML-MCTDH) techniques. The accuracy and efficiency of the new implementation of vMCG is directly compared with the method of coupled coherent states (CCS), another technique that uses trajectory guided grids. More generally we demonstrate that trajectory guided Gaussian based methods are capable of simulating quantum systems with tens or even hundreds of degrees of freedom previously accessible only for MCTDH and ML-MCTDH.