title: Highly Selective Relaxation of the OH Stretching Overtones in Isolated HDO Molecules Observed by Infrared Pump-Repump-Probe Spectroscopy.
abstract: A quantitative investigation of the relaxation dynamics of higher-lying vibrational states is afforded by a novel method of infrared pump-repump-probe spectroscopy. The technique is used to study the dynamics of OH stretching overtones in NaClO4·HDO monohydrate. We observe a continuous decrease of the energy separation for the first four states, i.e. v01 = 3575 cm(-1), v12 = 3370 cm(-1), and v23 = 3170 cm(-1), respectively. The population lifetime of the first excited state is 7.2 ps, while the one of the second excited state is largely reduced to 1.4 ps. The relaxation of the v = 2 state proceeds nearly quantitatively to the v = 1 state. The new information on the OH stretching overtones demands improved theoretical potentials and modeling of the H bond interactions. This work shows the potential of the new technique for the precise study of complex vibrational relaxation pathways.
authors.affiliation: †Physik-Department, Technische Universität München, James-Franck-Strasse, D-85748 Garching, Germany.
authors.forename: Daniel
authors.initials: D
authors.lastname: Hutzler
authors.affiliation: †Physik-Department, Technische Universität München, James-Franck-Strasse, D-85748 Garching, Germany.
authors.forename: Jasper C
authors.initials: JC
authors.lastname: Werhahn
authors.affiliation: †Physik-Department, Technische Universität München, James-Franck-Strasse, D-85748 Garching, Germany.
authors.forename: Rupert
authors.initials: R
authors.lastname: Heider
authors.affiliation: ‡Lehrstuhl für BioMolekulare Optik, Ludwig-Maximilians-Universität München, Oettingenstraße 67, D-80538 Munich, Germany.
authors.forename: Maximilian
authors.initials: M
authors.lastname: Bradler
authors.affiliation: †Physik-Department, Technische Universität München, James-Franck-Strasse, D-85748 Garching, Germany.
authors.forename: Reinhard
authors.initials: R
authors.lastname: Kienberger
authors.affiliation: ‡Lehrstuhl für BioMolekulare Optik, Ludwig-Maximilians-Universität München, Oettingenstraße 67, D-80538 Munich, Germany.
authors.forename: Eberhard
authors.initials: E
authors.lastname: Riedle
authors.affiliation: †Physik-Department, Technische Universität München, James-Franck-Strasse, D-85748 Garching, Germany.
authors.forename: Hristo
authors.initials: H
authors.lastname: Iglev
mesh_terms: D003510:Cyclohexanes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D006860:Hydrogen Bonding; D007094:Imides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D010472:Perchlorates / Q000737:chemistry; D017670:Sodium Compounds / Q000737:chemistry; D013055:Spectrophotometry, Infrared / Q000379:methods*; D014732:Vibration
chemical_list: D003510:Cyclohexanes; D007094:Imides; C469872:N-cyclohexyl-diazeniumdioxide; D010472:Perchlorates; D017670:Sodium Compounds; D006859:Hydrogen; C031068:sodium perchlorate; D010100:Oxygen