title: First principles semiclassical calculations of vibrational eigenfunctions.
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 CO(2) 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.
authors.affiliation: Dipartimento di Chimica Fisica ed Elettrochimica, Università degli Studi di Milano, via Golgi 19, 20133 Milano, Italy. michele.ceotto@unimi.it
authors.forename: Michele
authors.initials: M
authors.lastname: Ceotto
authors.forename: Stéphanie
authors.initials: S
authors.lastname: Valleau
authors.forename: Gian Franco
authors.initials: GF
authors.lastname: Tantardini
authors.forename: Alán
authors.initials: A
authors.lastname: Aspuru-Guzik