Fast mode-to-mode vibrational energy transfer in D2CO vapour: analysis of a complex pressure dependence

C. P. Bewick*, B. J. Orr

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)


The kinetics of fast, rotationally specific vibrational energy transfer between the ν6 and ν4 vibrational modes of D2CO displays a complex pressure dependence, which is suggestive of a unimolecular contribution to the ν6→ν4 transfer mechanism. This interpretation is discredited on the basis of an insufficient density of states of the low-energy portion of the (ν4, ν6) rovibrational manifold. The apparent anomaly is satisfactorily explained by detailed kinetic modelling which takes account of the finite duration of the pulsed infrared excitation and of the multi-channel nature of the collision-induced ν6→ν4 transfer mechanism.

Original languageEnglish
Pages (from-to)66-72
Number of pages7
JournalChemical Physics Letters
Issue number1
Publication statusPublished - 30 Jun 1989

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