title: Femtosecond stimulated Raman spectroscopy as a tool to detect molecular vibrations in ground and excited electronic states.
abstract: We give a detailed theoretical analysis of the simplest variant of femtosecond stimulated Raman spectroscopy, where a picosecond Raman pump pulse and a femtosecond Raman probe pulse are applied resonantly to a chromophore in thermal equilibrium in the ground electronic state. We demonstrate that this technique is capable of the detection of dephasing-free Raman-like lines revealing vibrational modes not only in the electronic ground state but also in the excited electronic state of the chromophore. The analytical results obtained with simplifying assumptions for the shape of the laser pulses are substantiated by numerical simulations with realistic laser pulses, employing the equation-of-motion phase-matching approach.
authors.affiliation: Department of Chemistry, Technische Universität München, D-85747 Garching, Germany.
authors.forename: Maxim F
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
authors.affiliation: Departamento de Química and Centro de Química, Universidade de Coimbra, 3004-535 Coimbra, Portugal.
authors.forename: B Jayachander
authors.initials: BJ
authors.lastname: Rao