Multidimensional Tunneling Dynamics Employing Quantum-Trajectory Guided Adaptable Gaussian Bases

Abstract

An efficient basis representation of time-dependent wavefunctions is essential for theoretical studies of high-dimensional molecular systems exhibiting large-amplitude motion. For fully coupled anharmonic systems, the complexity of a general wavefunction scales exponentially with the system size; therefore, for practical reasons, it is desirable to adapt the basis to the time-dependent wavefunction at hand. Often times on this quest for a minimal basis representation, time-dependent Gaussians are employed, in part because of their localization in both configuration and momentum spaces and also because of their direct connection to classical and semiclassical dynamics, guiding the evolution of the basis function parameters. In this work, the quantum-trajectory guided adaptable Gaussian (QTAG) bases method [J. Chem. Theory Comput.2020161834] is generalized to include correlated, i.e., non-factorizable, basis functions, and the performance of the QTAG dynamics is assessed on benchmark system/bath tunneling models of up to 20 dimensions. For the popular choice of initial conditions describing tunneling between the reactant/product wells, the minimal “semiclassical” description of the bath modes using essentially a single multidimensional basis function combined with the multi-Gaussian representation of the tunneling mode is shown to capture the dominant features of dynamics in a highly efficient manner.

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