title: SHARC: ab Initio Molecular Dynamics with Surface Hopping in the Adiabatic Representation Including Arbitrary Couplings.
abstract: We present a semiclassical surface-hopping method which is able to treat arbitrary couplings in molecular systems including all degrees of freedom. A reformulation of the standard surface-hopping scheme in terms of a unitary transformation matrix allows for the description of interactions like spin-orbit coupling or transitions induced by laser fields. The accuracy of our method is demonstrated in two systems. The first one, consisting of two model electronic states, validates the semiclassical approach in the presence of an electric field. In the second one, the dynamics in the IBr molecule in the presence of spin-orbit coupling after laser excitation is investigated. Due to an avoided crossing that originates from spin-orbit coupling, IBr dissociates into two channels: I + Br((2)P3/2) and I + Br*((2)P1/2). In both systems, the obtained results are in very good agreement with those calculated from exact quantum dynamical simulations.
authors.affiliation: Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, Helmholtzweg 4, 07743 Jena, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Richter
authors.affiliation: Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, Helmholtzweg 4, 07743 Jena, Germany.
authors.forename: Philipp
authors.initials: P
authors.lastname: Marquetand
authors.affiliation: Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, Helmholtzweg 4, 07743 Jena, Germany.
authors.forename: Jesús
authors.initials: J
authors.lastname: González-Vázquez
authors.affiliation: Departamento de Química Física I, Universidad Complutense, 28040 Madrid, Spain.
authors.forename: Ignacio
authors.initials: I
authors.lastname: Sola
authors.affiliation: Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, Helmholtzweg 4, 07743 Jena, Germany.
authors.forename: Leticia
authors.initials: L
authors.lastname: González