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.

“Divide-and-conquer” semiclassical molecular dynamics : An application to water clusters / G. Di Liberto, R. Conte, M. Ceotto. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 148:10(2018 Mar 14), pp. 104302.104302-1-104302.104302-12. [10.1063/1.5023155]

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

G. Di Liberto
Primo
;
R. Conte
Penultimo
;
M. Ceotto
Ultimo
2018

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.
semiclassical; water cluster; IR spectroscopy
Settore CHIM/02 - Chimica Fisica
   Divide and Conquer ad initio semiclassical molecular dynamics for spectropic calculations of complex systems (SEMICOMPLEX)
   SEMICOMPLEX
   EUROPEAN COMMISSION
   H2020
   647107
14-mar-2018
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/561903
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