Symmetry-breaking collisional energy transfer in the 4 νcH rovibrational manifold of acetylene

Spectroscopic evidence of a quasi-continuum of background states

Mark A. Payne, Angela P. Milce, Michael J Frost, Brian J. Orr

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Collision-induced molecular energy transfer in the 12700 cm-1 '4νCH' rovibrational manifold of acetylene is studied by infrared-ultraviolet double-resonance spectroscopy. As in previous work, there is evidence of (formally forbidden) odd-numbered changes in rotational quantum number J. Such 'symmetry-breaking' processes are invariant to choice of fluorescence-monitored vibronic band. The prominent (10300)0 J=12 rovibrational state appears to be a likely gateway and is rationalised in terms of a combination of quasi-resonant Coriolis and Stark mixing. An unusual collision-induced quasi-continuous background, underlying the discrete rovibrational states of the 4νCH manifold, offers a mechanistic key to the apparent symmetry breaking.

Original languageEnglish
Pages (from-to)48-56
Number of pages9
JournalChemical Physics Letters
Volume324
Issue number1-3
DOIs
Publication statusPublished - 30 Jun 2000

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