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dc.contributor.authorYang, SKen_US
dc.contributor.authorLiu, SYen_US
dc.contributor.authorChen, HFen_US
dc.contributor.authorLee, YPen_US
dc.date.accessioned2014-12-08T15:17:53Z-
dc.date.available2014-12-08T15:17:53Z-
dc.date.issued2005-12-08en_US
dc.identifier.issn0021-9606en_US
dc.identifier.urihttp://dx.doi.org/10.1063/1.2131072en_US
dc.identifier.urihttp://hdl.handle.net/11536/12972-
dc.description.abstractFollowing the photodissociation of o-fluorotoluene [o-C6H4(CH3)F] at 193 nm, rotationally resolved emission spectra of HF(1 <= v <= 4) in the spectral region of 2800-4000 cm(-1) are detected with a step-scan Fourier transform spectrometer. HF(v <= 4) shows nearly Boltzmann-type rotational distributions corresponding to a temperature similar to 1080 K; a short extrapolation from data in the period of 0.5-4.5 mu s leads to a nascent rotational temperature of 1130 +/- 100 K with an average rotational energy of 9 +/- 2 kJ mol(-1). The observed vibrational distribution of (v=1):(v=2):(v=3)=67.6: 23.2: 9.2 corresponds to a vibrational temperature of 5330 +/- 270 K. An average vibrational energy of 25 +/-(12)(3) kJ mol(-1) is derived based on the observed population of HF(1 <= v <= 3) and estimates of the population of HF (v=0 and 4) by extrapolation. Experiments performed on p-fluorotoluene [p-C6H4(CH3)F] yielded similar results with an average rotational energy of 9 +/- 2 kJ mol(-1) and vibrational energy of 26 +/-(12)(3) kJ mol(-1) for HF. The observed distributions of internal energy of HF in both cases are consistent with that expected for four-center elimination. A modified impulse model taking into account geometries and displacement vectors of transition states during bond breaking predicts satisfactorily the rotational excitation of HF. An observed vibrational energy of HF produced from fluorotoluene slightly smaller than that from fluorobenzene might indicate the involvement of seven-membered-ring isomers upon photolysis. (c) American Institute of Physics.en_US
dc.language.isoen_USen_US
dc.titleMolecular elimination in photolysis of o- and p-fluorotoluene at 193 nm: Internal energy of HF determined with time-resolved Fourier transform spectroscopyen_US
dc.typeArticleen_US
dc.identifier.doi10.1063/1.2131072en_US
dc.identifier.journalJOURNAL OF CHEMICAL PHYSICSen_US
dc.citation.volume123en_US
dc.citation.issue22en_US
dc.citation.epageen_US
dc.contributor.department應用化學系zh_TW
dc.contributor.department應用化學系分子科學碩博班zh_TW
dc.contributor.departmentDepartment of Applied Chemistryen_US
dc.contributor.departmentInstitute of Molecular scienceen_US
dc.identifier.wosnumberWOS:000234120800016-
dc.citation.woscount9-
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