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Polarization-detected transient gain studies of relaxation processes in v4=1 A-tilde 1A2 formaldehyde-h2

J. Chem. Phys. 88, 4819 (1988); doi:10.1063/1.454694

Issue Date: 15 April 1988

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P. H. Vaccaro, F. Temps, S. Halle, J. L. Kinsey, and R. W. Field
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139
Polarization-detected transient gain spectroscopy (PTGS), a time-resolved PUMP/PROBE scheme with single rotation–vibration level selectivity in both preparative and monitoring stages, has been used to study total depopulation and rotational state-to-state rates in the H2CO A-tilde 1A2 v4=1 vibrational level. For H2CO(A-tilde)/H2CO(X-tilde) collisions, single rovibronic level depopulation rates in the range 88±2 to 127±6 µs−1 Torr−1 (~10 times faster than the hard sphere gas kinetic rate) were obtained from Stern–Volmer plots which were found to be linear over at least the 0.02–0.2 Torr pressure region. Rotational relaxation between the 50,5 and 60,6 eigenstates reflects a-dipole propensity rules with the sum of first order DeltaJ=+1 and DeltaJ=−1 processes accounting for well over 50% of the total removal cross section measured for a single rovibronic level. The agreement between collisional decay rates for the 132,12 eigenstate measured previously by the TGS technique and here by PTGS, 110±3 and 106±4 µs−1 Torr−1, respectively, suggests that elastic reorientation processes (DeltaJ=DeltaKa =DeltaKc =0, DeltaM[not-equal]0) occur with much less efficiency than inelastic energy transfer. Collisional depopulation from single rotational levels of H2CO A-tilde 1A2 v4=1 is a remarkably efficient process, but completely understandable in the small molecule, isolated binary collision limit. None of the multiexponential decay and nonlinear Stern–Volmer effects manifest in previous undispersed fluorescence studies remain when PTGS is used to populate and monitor a single rovibronic level. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 6 October 1987; accepted 22 December 1987
Permalink: http://link.aip.org/link/?JCPSA6/88/4819/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.50.Dq
    Molecular spectra and interactions of molecules with photons Fluorescence and phosphorescence; radiationless transitions (intersystem crossing, internal conversion) Fluorescence and phosphorescence spectra
  • YEAR: 1988

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0021-9606 (print)   1089-7690 (online)
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