title: Local Control Theory in Trajectory Surface Hopping Dynamics Applied to the Excited-State Proton Transfer of 4-Hydroxyacridine.
abstract: The application of local control theory combined with nonadiabatic ab initio molecular dynamics to study the photoinduced intramolecular proton transfer reaction in 4-hydroxyacridine was investigated. All calculations were performed within the framework of linear-response time-dependent density functional theory. The computed pulses revealed important information about the underlying excited-state nuclear dynamics highlighting the involvement of collective vibrational modes that would normally be neglected in a study performed on model systems constrained to a subset of the full configuration space. This study emphasizes the strengths of local control theory for the design of pulses that can trigger chemical reactions associated with the population of a given molecular excited state. In addition, analysis of the generated pulses can help to shed new light on the photophysics and photochemistry of complex molecular systems.
authors.affiliation: Laboratory of Computational Chemistry and Biochemistry, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne (Switzerland).|Current address: Department of Chemistry, Stanford University, Stanford, California 94305 (USA).
authors.forename: Basile F E
authors.initials: BF
authors.lastname: Curchod
authors.affiliation: SwissFEL, Paul Scherrer Inst. 5232 Villigen (Switzerland). thomas.penfold@psi.ch.
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Penfold
authors.affiliation: Laboratory of Computational Chemistry and Biochemistry, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne (Switzerland).
authors.forename: Ursula
authors.initials: U
authors.lastname: Rothlisberger
authors.affiliation: Laboratory of Computational Chemistry and Biochemistry, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne (Switzerland). ita@zurich.ibm.com.|Current address: IBM Research GmbH, Zurich Research Laboratory, 8803 Rüschlikon (Switzerland). ita@zurich.ibm.com.
authors.forename: Ivano
authors.initials: I
authors.lastname: Tavernelli
keywords: density functional calculations; local control theory; molecular dynamics; photophysics; proton transfer