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Vibrational dynamics of pyrrole via frequency-domain spectroscopy

Source: J. Chem. Phys. 136, 024313 (2012); http://dx.doi.org/10.1063/1.3673614

Published 10 January 2012

KEYWORDS and PACS
Keywords
PACS
  • 33.15.Hp
    Molecular barrier heights (internal rotation, inversion, rotational isomerism, conformational dynamics)
  • 33.15.Mt
    Molecular rotation, vibration, and vibration-rotation constants
  • YEAR: 2011
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PUBLICATION DATA
ISSN:
1553-9628 (online)
Publisher:
AIP is a member of CrossRef AIP
Alexander Portnov, Michael Epshtein, Salman Rosenwaks, and Ilana Bar
Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel
The N–H stretch overtones of pyrrole, a key constituent of biologic building blocks, were studied by room temperature photoacoustic and jet-cooled action spectroscopies to unravel their intramolecular dynamics. Contrary to “isolated” states excited with two and three N–H stretch quanta, the one with four quanta shows strong accidental resonances with two other states involving three quanta of N–H stretch and one quantum of C–H stretch. The inhomogeneously reduced features in the action spectra provide the means for getting insight into the intramolecular interactions and the factors controlling energy flow within pyrrole. The time dependence of the survival probability of the 4nu1 N–H stretch, deduced from the vibrational Hamiltonian, shows an initial decay in ~0.3 ps with ensuing quantum beats from the N–H – C–H resonance and their decay with a time constant of about 5 ps as a result of weaker coupling to bath states. ©2012 American Institute of Physics
History: Received 26 October 2011; accepted 8 December 2011; published 10 January 2012
Digital Object Identifier: http://dx.doi.org/10.1063/1.3673614

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