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Article: Gas-phase chloroiodomethane short-time photodissociation dynamics in the A-band absorption and a comparison with the solution phase short-time photodissociation dynamics

TitleGas-phase chloroiodomethane short-time photodissociation dynamics in the A-band absorption and a comparison with the solution phase short-time photodissociation dynamics
Authors
Issue Date1997
PublisherTaylor & Francis Ltd. The Journal's web site is located at http://www.tandf.co.uk/journals/titles/00268976.asp
Citation
Molecular Physics, 1997, v. 90 n. 3, p. 315-326 How to Cite?
AbstractA gas-phase resonance Raman spectrum of chloroiodomethane has been obtained with excitation in the A-band absorption with similar resolution and the same experimental apparatus used to obtain solution-phase A-band resonance Raman spectra of chloroiodomethane reported previously. This allows a careful and detailed comparison of the gas-and solution-phase chloroiodomethane A-band resonance Raman spectra and their associated short-time photodissociation dynamics. The gas-phase A-band resonance Raman spectrum has four Franck-Condon active vibrational modes and a noticeable degree of multidimensionality in its photodissociation reaction. The A-band gas-phase resonance Raman intensities and absorption spectrum were simulated using a simple model and time-dependent wave-packet calculations. The motion of the wave packet on the excited state gas-phase potential surface was converted from dimensionless normal coordinates into easy-to-visualize internal coordinates using the results of normal coordinate calculations. The A-band early-time photodissociation dynamics are very similar to those of the solution phase in that the C-I bond lengthens, the I-C-Cl and H-C-I angles become smaller, and the H-C-Cl angles become larger. These short-time photodissociation dynamics are consistent with a simple impulsive 'semirigid' radical model description of the photodissociation. A comparison of the gas-phase and solution-phase short-time photodissociation dynamics suggests that solvation effects are not important for internal coordinate motions such as the C-I stretch and I-C-Cl angle where there are strong intramolecular forces but that solvation effects are noticeable for internal coordinate motions such as H-C-H angle and H-C-Cl angles which are weakly involved in the dissociation coordinate and have relatively weak intramolecular forces that are more easily perturbed by the solvent-solute forces. This implies that 'static' or mean-field solvation effects may be more significant for internal coordinate motions that have small intramolecular forces compared with internal coordinate motions that have much larger intramolecular forces from the photodissociation reaction.
Persistent Identifierhttp://hdl.handle.net/10722/69821
ISSN
2015 Impact Factor: 1.837
2015 SCImago Journal Rankings: 0.781
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorKwok, WMen_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2010-09-06T06:17:08Z-
dc.date.available2010-09-06T06:17:08Z-
dc.date.issued1997en_HK
dc.identifier.citationMolecular Physics, 1997, v. 90 n. 3, p. 315-326en_HK
dc.identifier.issn0026-8976en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69821-
dc.description.abstractA gas-phase resonance Raman spectrum of chloroiodomethane has been obtained with excitation in the A-band absorption with similar resolution and the same experimental apparatus used to obtain solution-phase A-band resonance Raman spectra of chloroiodomethane reported previously. This allows a careful and detailed comparison of the gas-and solution-phase chloroiodomethane A-band resonance Raman spectra and their associated short-time photodissociation dynamics. The gas-phase A-band resonance Raman spectrum has four Franck-Condon active vibrational modes and a noticeable degree of multidimensionality in its photodissociation reaction. The A-band gas-phase resonance Raman intensities and absorption spectrum were simulated using a simple model and time-dependent wave-packet calculations. The motion of the wave packet on the excited state gas-phase potential surface was converted from dimensionless normal coordinates into easy-to-visualize internal coordinates using the results of normal coordinate calculations. The A-band early-time photodissociation dynamics are very similar to those of the solution phase in that the C-I bond lengthens, the I-C-Cl and H-C-I angles become smaller, and the H-C-Cl angles become larger. These short-time photodissociation dynamics are consistent with a simple impulsive 'semirigid' radical model description of the photodissociation. A comparison of the gas-phase and solution-phase short-time photodissociation dynamics suggests that solvation effects are not important for internal coordinate motions such as the C-I stretch and I-C-Cl angle where there are strong intramolecular forces but that solvation effects are noticeable for internal coordinate motions such as H-C-H angle and H-C-Cl angles which are weakly involved in the dissociation coordinate and have relatively weak intramolecular forces that are more easily perturbed by the solvent-solute forces. This implies that 'static' or mean-field solvation effects may be more significant for internal coordinate motions that have small intramolecular forces compared with internal coordinate motions that have much larger intramolecular forces from the photodissociation reaction.en_HK
dc.languageengen_HK
dc.publisherTaylor & Francis Ltd. The Journal's web site is located at http://www.tandf.co.uk/journals/titles/00268976.aspen_HK
dc.relation.ispartofMolecular Physicsen_HK
dc.titleGas-phase chloroiodomethane short-time photodissociation dynamics in the A-band absorption and a comparison with the solution phase short-time photodissociation dynamicsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0026-8976&volume=90&issue=3&spage=315&epage=326&date=1997&atitle=Gas-phase+chloroiodomethane+short-time+photodissociation+dynamics+in+the+A-band+absorption+and+a+comparison+with+the+solution+phase+short-time+photodissociation+dynamicsen_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1080/002689797172444-
dc.identifier.scopuseid_2-s2.0-0000953827en_HK
dc.identifier.hkuros24373en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0000953827&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume90en_HK
dc.identifier.issue3en_HK
dc.identifier.spage315en_HK
dc.identifier.epage326en_HK
dc.identifier.isiWOS:A1997WK75400002-
dc.publisher.placeUnited Kingdomen_HK
dc.identifier.scopusauthoridKwok, WM=7103129332en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK

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