Vibrational eigenfunctions are calculated on-the-fly using semiclassical methods in conjunction with ab initio density functional theory classical trajectories. Various semiclassical approximations based on the time-dependent representation of the eigenfunctions are tested on an analytical potential describing the chemisorption of CO on Cu(100). Then, first principles semiclassical vibrational eigenfunctions are calculated for the CO2 molecule and its accuracy evaluated. The multiple coherent states initial value representations semiclassical method recently developed by us has shown with only six ab initio trajectories to evaluate eigenvalues and eigenfunctions at the accuracy level of thousands trajectory semiclassical initial value representation simulations.

First principles semiclassical calculations of vibrational eigenfunctions / M. Ceotto, S. Valleau, G.F. Tantardini, A. Aspuru Guzik. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 134:23(2011 Jun 17), pp. 234103.234103-1-234103.234103-12.

First principles semiclassical calculations of vibrational eigenfunctions

M. Ceotto;G.F. Tantardini;
2011-06-17

Abstract

Vibrational eigenfunctions are calculated on-the-fly using semiclassical methods in conjunction with ab initio density functional theory classical trajectories. Various semiclassical approximations based on the time-dependent representation of the eigenfunctions are tested on an analytical potential describing the chemisorption of CO on Cu(100). Then, first principles semiclassical vibrational eigenfunctions are calculated for the CO2 molecule and its accuracy evaluated. The multiple coherent states initial value representations semiclassical method recently developed by us has shown with only six ab initio trajectories to evaluate eigenvalues and eigenfunctions at the accuracy level of thousands trajectory semiclassical initial value representation simulations.
semiclassical; vibrational; DFT; eigenfunction; first principles; ab initio; molecular dynamics
Settore CHIM/02 - Chimica Fisica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/159818
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