Intramolecular dynamics from frequency domain spectroscopy

Alexander Portnov, Yuval Ganot, Evgeny Bespachiansky, Salman Rosenwaks, Ilana Bar

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

Vibrationally mediated photodissociation is emerging as a useful tool for studies of intramolecular dynamics in polyatomic molecules since it is a sensitive indicator of both the vibrational and electronic dynamics. The method involves energy deposition in skeletal motions of molecules, their subsequent promotion to excited electronic states and dissociation. Jet-cooled action spectra, reflecting the yield of the ensuing atomic fragments as a function of vibrational excitation, are compared to simultaneously measured room temperature photoacoustic spectra and simulated spectra. The narrowed action spectra expose resonance splitting and enable estimating the homogeneous broadening and thus time scales for intramolecular vibrational energy redistribution to close resonating states and to bath states. Overtone spectra of the acetylenic and alkyl C{single bond}H stretches of the acetylene homologues, propyne and 1-butyne, demonstrate how the nature of rovibrationally excited states is highlighted by photolysis of pre-excited molecules.

Original languageEnglish
Pages (from-to)147-155
Number of pages9
JournalVibrational Spectroscopy
Volume42
Issue number1
DOIs
StatePublished - 18 Oct 2006

Keywords

  • Butyne
  • Intramolecular dynamics
  • Propyne
  • Vibrationally mediated photodissociation

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