title: A vibronic coupling hamiltonian to describe the ultrafast excited state dynamics of a Cu(i)-phenanthroline complex.
abstract: We present a model Hamiltonian to study the nonadiabatic dynamics of photoexcited [Cu(dmp)2](+), (dmp = 2,9-dimethyl-1,10-phenanthroline). The relevant normal modes, identified by the magnitude of the first order coupling constants, correspond closely to those observed experimentally. The potential energy surfaces (PES) and nonadiabatic couplings for these modes are computed and provide a first interpretation of the nonadiabatic relaxation mechanism. The Hamiltonian incorporates both the low lying singlet and triplet states, which will make it possible to follow the dynamics from the photoexcitation event to the initial stages of intersystem crossing.
authors.affiliation: Laboratory of Computational Chemistry and Biochemistry Ecole Polytechnique Fédérale de Lausanne CH-1015 Lausanne, Switzerland; Laboratory of Ultrafast Spectroscopy Ecole Polytechnique Fédérale de Lausanne CH-1015 Lausanne, Switzerland.
authors.forename: Gloria
authors.initials: G
authors.lastname: Capano
authors.affiliation: SwissFEL Paul Scherrer Institute CH-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 CH-1015 Lausanne, Switzerland.
authors.forename: Ursula
authors.initials: U
authors.lastname: Röthlisberger
authors.affiliation: Laboratory of Computational Chemistry and Biochemistry Ecole Polytechnique Fédérale de Lausanne CH-1015 Lausanne, Switzerland.
authors.forename: Ivano
authors.initials: I
authors.lastname: Tavernelli