title: Impact of Vibrational Coherence on the Quantum Yield at a Conical Intersection.
abstract: We study the vibrationally coherent quantum dynamics of an electronic wave packet in the vicinity of a conical intersection within a three-state two-mode model. By transforming the coherent tuning and coupling modes into the bath, the underdamped dynamics of the resulting effective three-state model is solved efficiently by the numerically exact hierarchy equation of motion approach. The transient excited-state absorption and two-dimensional spectra reveal the impact of vibrational coherence on the relaxation pathways of the wave packet. We find that both the quantum yield and the isomerization rate are crucially influenced by the vibrational coherence of the wave packet. A less coherent wave packet can traverse the conical intersection more rapidly, while the resulting quantum yield is smaller. Finally, we show that repeated passages of the wave packet through the conical intersection can lead to measurable interference effects in the form of Stueckelberg oscillations.
authors.affiliation: I. Institut für Theoretische Physik, Universität Hamburg , Jungiusstraße 9, 20355 Hamburg, Germany.|Max Planck-Institute for the Structure and Dynamics of Matter , Luruper Chaussee 149, 22761 Hamburg, Germany.|The Hamburg Center for Ultrafast Imaging , Luruper Chaussee 149, 22761 Hamburg, Germany.
authors.forename: Hong-Guang
authors.initials: HG
authors.lastname: Duan
authors.affiliation: Max Planck-Institute for the Structure and Dynamics of Matter , Luruper Chaussee 149, 22761 Hamburg, Germany.|The Hamburg Center for Ultrafast Imaging , Luruper Chaussee 149, 22761 Hamburg, Germany.|The Departments of Chemistry and Physics, University of Toronto , 80 St. George Street, Toronto, M5S 3H6 Canada.
authors.forename: R J Dwayne
authors.initials: RJ
authors.lastname: Miller
authors.affiliation: I. Institut für Theoretische Physik, Universität Hamburg , Jungiusstraße 9, 20355 Hamburg, Germany.|The Hamburg Center for Ultrafast Imaging , Luruper Chaussee 149, 22761 Hamburg, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Thorwart