Vibrationally excited populations from IR‐multiphoton absorption. I. Absorbed energy and reaction yield measurements
dc.contributor.author | Zellweger, Jean‐michel | en_US |
dc.contributor.author | Brown, Trevor C. | en_US |
dc.contributor.author | Barker, John R. | en_US |
dc.date.accessioned | 2010-05-06T21:15:39Z | |
dc.date.available | 2010-05-06T21:15:39Z | |
dc.date.issued | 1985-12-15 | en_US |
dc.identifier.citation | Zellweger, Jean‐Michel; Brown, Trevor C.; Barker, John R. (1985). "Vibrationally excited populations from IR‐multiphoton absorption. I. Absorbed energy and reaction yield measurements." The Journal of Chemical Physics 83(12): 6251-6260. <http://hdl.handle.net/2027.42/69859> | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/69859 | |
dc.description.abstract | The molecule 1,1,2‐trifluroethane (TFE) was used in experiments to determine the population distribution of excited molecules produced by infrared multiphoton absorption induced by high power TEA CO2 lasers operating at 1079.85 cm−1 [9.6 μm R(22) line]. Optoacoustic measurements of absorbed laser power provided a measure of the mean energy of the population distribution, while very low pressure photolysis measurements of the collision‐free decomposition yield gave information about the high‐energy tail of the distribution. The experimental results were accurately simulated using a Master Equation model that incorporated Quack’s statistical–dynamical theory of infrared multiphoton absorption (cases B and C), RRKM unimolecular reactions (three channels), and collisional energy transfer. The computer simulations included known TFE molecular properties and only four adjustable parameters, which were very highly constrained in order to fit the experimental data. From the simulations, we conclude that the optical coupling matrix elements are dramatically reduced in magnitude for energies above the reaction thresholds. This effect is symptomatic of the vibrational anharmonicity due to the presence of the reaction channels, even in molecules that have not yet reacted, resulting in vibrational frequency shifts of the absorption lines out of resonance with the laser line. This effect is expected to be present and observable in other highly vibrationally excited molecules. | en_US |
dc.format.extent | 3102 bytes | |
dc.format.extent | 997172 bytes | |
dc.format.mimetype | text/plain | |
dc.format.mimetype | application/pdf | |
dc.publisher | The American Institute of Physics | en_US |
dc.rights | © The American Institute of Physics | en_US |
dc.title | Vibrationally excited populations from IR‐multiphoton absorption. I. Absorbed energy and reaction yield measurements | en_US |
dc.type | Article | en_US |
dc.subject.hlbsecondlevel | Physics | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Atmospheric and Oceanic Science, Space Physics Laboratory, University of Michigan, Ann Arbor, Michigan 48109‐2143 | en_US |
dc.contributor.affiliationother | Department of Chemical Kinetics, Chemical Physics Laboratory, SRI International, Menlo Park, California 94025 | en_US |
dc.contributor.affiliationother | Department of Chemical Engineering, University of Adelaide, Box 498, G.P.O., Adelaide, South Australia 5001 | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/69859/2/JCPSA6-83-12-6251-1.pdf | |
dc.identifier.doi | 10.1063/1.449574 | en_US |
dc.identifier.source | The Journal of Chemical Physics | en_US |
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dc.owningcollname | Physics, Department of |
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