title: Nonadiabatic Ensemble Simulations of cis-Stilbene and cis-Azobenzene Photoisomerization.
abstract: Structurally, stilbene and azobenzene molecules exist in closed and open cis and trans forms, which are able to transform into each other under the influence of light (photoisomerization). To accurately simulate the photoisomerization processes, one must go beyond ground-state (Born-Oppenheimer) calculations and include nonadiabatic coupling between the electronic and vibrational states. We have successfully implemented nonadiabatic couplings and a surface-hopping algorithm within a density functional theory approach that utilizes local orbitals. We demonstrate the effectiveness of our approach by performing molecular dynamics simulations of the cis-trans photoisomerization in both azobenzene and stilbene upon excitation into the S1 state. By generating an ensemble of trajectories, we can gather characteristic transformation times and quantum yields that we will discuss and compare with ultrafast spectroscopic experiments.
authors.affiliation: Department of Physics and Astronomy, University of Rochester , Rochester, New York 14627, United States.|Department of Physics and Astronomy, West Virginia University , Morgantown, West Virginia 26506-6315, United States.
authors.forename: Amanda J
authors.initials: AJ
authors.lastname: Neukirch
authors.affiliation: Department of Physics and Astronomy, West Virginia University , Morgantown, West Virginia 26506-6315, United States.
authors.forename: Logan C
authors.initials: LC
authors.lastname: Shamberger
authors.affiliation: Computational Biochemistry Group, Institute of Theoretical Chemistry, University of Stuttgart , 70569 Stuttgart, Germany.
authors.forename: Enrique
authors.initials: E
authors.lastname: Abad
authors.affiliation: Department of Physics and Astronomy, West Virginia University , Morgantown, West Virginia 26506-6315, United States.
authors.forename: Barry J
authors.initials: BJ
authors.lastname: Haycock
authors.affiliation: Department of Physics and Astronomy, West Virginia University , Morgantown, West Virginia 26506-6315, United States.
authors.forename: Hong
authors.initials: H
authors.lastname: Wang
authors.affiliation: Departmento de Física Teórica de la Materia Condensada and Conensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid , Madrid 28049, Spain.
authors.forename: José
authors.initials: J
authors.lastname: Ortega
authors.affiliation: Department of Physics and Astronomy, University of Rochester , Rochester, New York 14627, United States.|Department of Chemistry, University of Rochester , Rochester, New York 14627, United States.
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Prezhdo
authors.affiliation: Department of Physics and Astronomy, West Virginia University , Morgantown, West Virginia 26506-6315, United States.
authors.forename: James P
authors.initials: JP
authors.lastname: Lewis