Christopoulou, G; Freibert, A; Worth, GA; (2021) Improved algorithm for the direct dynamics variational multi-configurational Gaussian method. Journal of Chemical Physics , 154 (12) , Article 124127. 10.1063/5.0043720.

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Abstract

The Direct Dynamics variational Multi-Configurational Gaussian (DD-vMCG) method provides a fully quantum mechanical solution to the time-dependent Schrödinger equation for the time evolution of nuclei with potential surfaces calculated on-the-fly using a quantum chemistry program. Initial studies have shown its potential for flexible and accurate simulations of non-adiabatic excited-state molecular dynamics. In this paper, we present developments to the DD-vMCG algorithm that improve both its accuracy and efficiency. First, a new, efficient parallel algorithm to control the DD-vMCG database of quantum chemistry points is presented along with improvements to the Shepard interpolation scheme. Second, the use of symmetry in describing the potential surfaces is introduced along with a new phase convention in the propagation diabatization. Benchmark calculations on the allene radical cation including all degrees of freedom then show that the new scheme is able to produce a consistent non-adiabatic coupling vector field. This new DD-vMCG version thus opens the route for effectively and accurately treating complex chemical systems using quantum dynamics simulations.

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