title: Resonant femtosecond stimulated Raman spectroscopy with an intense actinic pump pulse: Application to conical intersections.
abstract: We theoretically investigate the feasibility of characterizing conical intersections with time-resolved resonant femtosecond stimulated Raman spectroscopy (FSRS) using an intense actinic pump pulse. We perform nonperturbative numerical simulations of FSRS signals for a three-electronic-state two-vibrational-mode model, which is inspired by the S2(ππ*)-S1(nπ*) conical intersection in pyrazine. Our results show that moderately strong actinic pulses increase the intensity of vibrational fingerprint lines in FSRS transients. They facilitate the extraction of useful spectroscopic information by enhancing peaks revealing the coupling and tuning modes of the conical intersection.
authors.affiliation: Department of Chemistry, Technische Universität München, D-85747 Garching, Germany.
authors.forename: B Jayachander
authors.initials: BJ
authors.lastname: Rao
authors.affiliation: Department of Chemistry, Technische Universität München, D-85747 Garching, Germany.
authors.forename: Maxim F
authors.identifier: 0000000330923343
authors.initials: MF
authors.lastname: Gelin
authors.affiliation: Department of Chemistry, Technische Universität München, D-85747 Garching, Germany.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Domcke