Observation of an energy threshold for large ΔE collisional relaxation of highly vibrationally excited pyrazine (Evib=31 000-41 000 cm-1) by CO2

Michael S. Elioff, Mark C. Wall, Andrew S. Lemoff, Amy S. Mullin

Research output: Contribution to journalArticle

28 Scopus citations

Abstract

Energy dependent studies of the collisional relaxation of highly vibrationally excited pyrazine through collisions with CO2 were performed for initial pyrazine energies Evib = 31 000-35 000 cm-1. These studies are presented along with earlier results for pyrazine with Evib= 36 000-41 000 cm-1. High-resolution transient IR laser absorption of individual CO2 (00°0) rotational states (J = 56-80) was used to investigate the magnitude and partitioning of energy gain into CO2 rotation and translation, which comprises the high energy tail of the energy transfer distribution function. Highly vibrationally excited pyrazine was prepared by absorption of pulsed UV light at seven wavelengths in the range λ = 281-324 nm, followed by radiationless decay to pyrazine's ground electronic state. Nascent CO2 (00°0) rotational populations were measured for each UV excitation wavelength and distributions of nascent recoil velocities for individual rotational states of CO2 (00°0) were obtained from Doppler-broadened transient linewidth measurements. Measurements of energy transfer rate constants at each UV wavelength yield energy-dependent probabilities for collisions involving large ΔE values. These results reveal that the magnitude of large ΔE collisional energy gain in CO2 (00°0) is fairly insensitive to the amount of vibrational energy in pyrazine for Evib= 31 000-35 000 cm-1. A comparison with earlier studies on pyrazine with Evib= 36 000-41 000 cm-1 indicates that the V→RT energy transfer increases both in magnitude and probability for Evib>36 000 cm-1. Implications of incomplete intramolecular vibrational relaxation, electronic state coupling, and isomerization barriers are discussed in light of these results.

Original languageEnglish (US)
Pages (from-to)5578-5588
Number of pages11
JournalJournal of Chemical Physics
Volume110
Issue number12
DOIs
StatePublished - Mar 22 1999

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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