Rotational energy transfer in D2CO (v4=1)

IR-UV double resonance studies of J-changing collisions

C. P. Bewick, J. G. Haub, R. G. Hynes, J. F. Martins, B. J. Orr*

*Corresponding author for this work

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The technique of time-resolved infrared-ultraviolet double resonance (IRUVDR) spectroscopy is used to characterize the rate and mechanism of state-to-state rotational energy transfer (RET) in D2CO/D 2CO collisions. The investigations employ C02-laser irradiation to prepare a D2CO molecule in the v4 = 1, (J,Ka) = (18,11) rovibrational level of its X̃1A 1 electronic ground state. Vapor-phase collisions with other D 2CO (v = 0) molecules then induce RET, with IRUVDR-monitored quantum-number changes ΔJ for the state-selected molecule ranging between +3 and -7. Kinetic modeling of the resulting experimental data shows that the inelastic cross sections for such J-changing rotational relaxation can be described adequately by simple scaling laws based on the rotational energy change \ΔE| for the state-selected molecule, with a power-gap fitting law proving marginally superior to an exponential-gap fitting law. The range of \ΔJ| monitored in these experiments is sufficiently extensive to discredit a simple propensity-rule fitting law, comprising consecutive collision-induced processes with individual changes \ΔJ\ confined to values of 1 or 2. The microscopic rate constants derived reflect the dominance of ΔJ = ± 1 contributions for J-changing RET in D2CO/D2CO collisions, owing to long-range dipole/dipole interactions. These results elucidate RET in collisions between a pair of dipolar polyatomic (D 2CO) molecules at a level of detail usually confined to studies of dipolar diatomic molecules, such as HF. Less detailed IRUVDR results, for RET in self-collisions of HDCO and for D2CO colliding with a variety of foreign-gas molecules, are also presented.

Original languageEnglish
Pages (from-to)6350-6371
Number of pages22
JournalThe Journal of Chemical Physics
Volume88
Issue number10
DOIs
Publication statusPublished - 1988
Externally publishedYes

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