'Divide-and-conquer' semiclassical molecular dynamics: An application to water clusters

Abstract

We present an investigation of vibrational features in water clusters performed by means of our recently established divide-and-conquer semiclassical approach [M. Ceotto, G. Di Liberto, and R. Conte, Phys. Rev. Lett. 119, 010401 (2017)]. This technique allows us to simulate quantum vibrational spectra of high-dimensional systems starting from full-dimensional classical trajectories and projection of the semiclassical propagator onto a set of lower dimensional subspaces. The potential energy surface employed is a many-body representation up to three-body terms, in which monomers and two-body interactions are described by the high level Wang-Huang-Braams-Bowman (WHBB) water potential, while, for three-body interactions, calculations adopt a fast permutationally invariant ab initio surface at the same level of theory of the WHBB 3-body potential. Applications range from the water dimer up to the water decamer, a system made of 84 vibrational degrees of freedom. Results are generally in agreement with previous variational estimates in the literature. This is particularly true for the bending and the high-frequency stretching motions, while estimates of modes strongly influenced by hydrogen bonding are red shifted, in a few instances even substantially, as a consequence of the dynamical and global picture provided by the semiclassical approach.

References in corpus (7)

• First-Principles Semiclassical Initial Value Representation Molecular Dynamics
• Semiclassical "Divide-and-Conquer" Method for Spectroscopic Calculations of High Dimensional Molecular Systems
• The Importance of the Pre-exponential Factor in Semiclassical Molecular Dynamics
• "Divide and Conquer" Semiclassical Molecular Dynamics: A practical method for Spectroscopic calculations of High Dimensional Molecular Systems
• Mixed Semiclassical Initial Value Representation Time-Averaging Propagator for Spectroscopic Calculations
• Graphics processing units accelerated semiclassical initial value representation molecular dynamics
• Application of the Mixed Time-averaging Semiclassical Initial Value Representation method to Complex Molecular Spectra

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