title: Nuclear Motion Driven Ultrafast Photodissociative Charge Transfer of the PENNA Cation: An Experimental and Computational Study.
abstract: Ultrafast nuclear driven charge transfer prior to dissociation is an important process in modular systems as was demonstrated experimentally in the bifunctional molecule 2-phenylethyl-N,N-dimethylamine (PENNA) in work by Lehr et al. ( J. Phys. Chem. A 2005 , 109 , 8074 ). The ultrafast dynamics of PENNA photoexcited to the three lowest electronic states of the cation (D0, D1, and D2) was studied using quantum chemistry and surface hoping. We show that a conical intersection, localized in the Franck-Condon region, between the D0and the D1states, leads to an ultrafast charge transfer, computed here to be on a time scale of 65 fs, between the phenyl and the amine charged subunits. On the D0ground state, the dissociation proceeds on the 60 ps time scale through a 19 kcal/mol late barrier. The computed kinetic energy release is in good agreement with a new experimental measurement of PENNA ionization by an 800 nm 30 fs intense laser pulse.
authors.affiliation: Department of Chemistry, B6c, University of Liege , B4000 Liege, Belgium.
authors.forename: Shoutian
authors.initials: S
authors.lastname: Sun
authors.affiliation: Department of Chemistry, B6c, University of Liege , B4000 Liege, Belgium.
authors.forename: Benoit
authors.initials: B
authors.lastname: Mignolet
authors.affiliation: Department of Chemistry, Wayne State University , Detroit, Michigan 48202, United States.
authors.forename: Lin
authors.initials: L
authors.lastname: Fan
authors.affiliation: Department of Chemistry, Wayne State University , Detroit, Michigan 48202, United States.
authors.forename: Wen
authors.initials: W
authors.lastname: Li
authors.affiliation: Crump Institute for Molecular Imaging and Department of Molecular and Medical Pharmacology, David Geffen School of Medicine, and Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.|The Fritz Haber Research Center for Molecular Dynamics, Institute of Chemistry, The Hebrew University of Jerusalem , 91904 Jerusalem, Israel.
authors.forename: Raphael D
authors.initials: RD
authors.lastname: Levine
authors.affiliation: Department of Chemistry, B6c, University of Liege , B4000 Liege, Belgium.
authors.forename: Francoise
authors.identifier: http://orcid.org/0000-0001-7434-5245
authors.initials: F
authors.lastname: Remacle