Intramolecular electronic coupling enhanced collisional deactivation of highly vibrationally excited molecules
- Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323 (United States)
The collisional deactivation of highly vibrationally excited NO{sub 2} and CS{sub 2} by a variety of buffer gases has been examined by time-resolved Fourier transform IR emission spectroscopy. The results show that there is a dramatic increase in the average energy removed per collision for NO{sub 2} excited above {similar_to}10 000 cm{sup {minus}1} and for CS{sub 2} above {similar_to}26 000 cm{sup {minus}1}. These energies correspond to the origins of the lowest excited {ital {tilde A}} {sup 2}{ital B}{sub 2}/{ital {tilde B}} {sup 2}{ital B}{sub 1} states of NO{sub 2} and the lowest excited {ital R} {sup 3}{ital A}{sub 2} state of CS{sub 2}. Mixing between these excited electronic states with the ground electronic state enhances collisional relaxation by allowing the electronic transition dipole to contribute to collisional energy transfer.
- DOE Contract Number:
- FG02-86ER13584
- OSTI ID:
- 46443
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 21 Vol. 102; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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