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Article: Picosecond time-resolved resonance Raman observation of the iso-CH2I–I photoproduct from the 'photoisomerization' reaction of diiodomethane in the solution phase

TitlePicosecond time-resolved resonance Raman observation of the iso-CH2I–I photoproduct from the 'photoisomerization' reaction of diiodomethane in the solution phase
Authors
KeywordsPhysics chemistry
Issue Date2000
PublisherAmerican Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jsp
Citation
Journal of Chemical Physics, 2000, v. 113 n. 17, p. 7471-7478 How to Cite?
AbstractWe report a preliminary picosecond Stokes and anti-Stokes time-resolved resonance Raman (267 nm pump and 400 nm probe excitation wavelengths) investigation of the initial formation and vibrational cooling of the iso-CH2I–I photoproduct species produced after ultraviolet excitation of diiodomethane in room temperature solutions. A comparison of the picosecond resonance Raman spectra with previously reported nanosecond transient resonance Raman spectra and density functional theory computations shows that the iso-CH2I–I photoproduct species is predominantly responsible for the ~385 nm transient absorption band observed from several picoseconds to nanoseconds after ultraviolet excitation of diiodomethane in the solution phase. Similar results were obtained in both nonpolar solution (cyclohexane solvent) and polar solution (acetonitrile) solvent. The picosecond resonance Raman spectra confirm that the iso-CH2I–I photoproduct species is formed vibrationally hot within several picoseconds and then subsequently undergoes vibrational cooling on the 4–50 ps time scale. This is consistent with the absorption bands changes occurring over similar times in a recent femtosecond transient absorption study. We discuss a possible qualitative scenario for the formation of the iso-CH2I–I species that is in agreement with the available gas phase experimental results for the ultraviolet photodissociation reaction of diiodomethane and gas phase collisional deactivation studies of the CH2I radical. The proposed hypothesis is consistent with the lack of distinct resonance Raman bands in the first few picoseconds of our solution phase spectra of the iso-CH2I–I photoproduct as well as previously reported femtosecond transient absorption bands that are broad and weak in the 300–500 nm region over the 0.3–3 ps time scale. © 2000 American Institute of Physics.
Persistent Identifierhttp://hdl.handle.net/10722/42351
ISSN
2015 Impact Factor: 2.894
2015 SCImago Journal Rankings: 0.959
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorKwok, WMen_HK
dc.contributor.authorMa, Cen_HK
dc.contributor.authorParker, AWen_HK
dc.contributor.authorPhillips, Den_HK
dc.contributor.authorTowrie, Men_HK
dc.contributor.authorMatousek, Pen_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2007-01-29T08:47:34Z-
dc.date.available2007-01-29T08:47:34Z-
dc.date.issued2000en_HK
dc.identifier.citationJournal of Chemical Physics, 2000, v. 113 n. 17, p. 7471-7478en_HK
dc.identifier.issn0021-9606en_HK
dc.identifier.urihttp://hdl.handle.net/10722/42351-
dc.description.abstractWe report a preliminary picosecond Stokes and anti-Stokes time-resolved resonance Raman (267 nm pump and 400 nm probe excitation wavelengths) investigation of the initial formation and vibrational cooling of the iso-CH2I–I photoproduct species produced after ultraviolet excitation of diiodomethane in room temperature solutions. A comparison of the picosecond resonance Raman spectra with previously reported nanosecond transient resonance Raman spectra and density functional theory computations shows that the iso-CH2I–I photoproduct species is predominantly responsible for the ~385 nm transient absorption band observed from several picoseconds to nanoseconds after ultraviolet excitation of diiodomethane in the solution phase. Similar results were obtained in both nonpolar solution (cyclohexane solvent) and polar solution (acetonitrile) solvent. The picosecond resonance Raman spectra confirm that the iso-CH2I–I photoproduct species is formed vibrationally hot within several picoseconds and then subsequently undergoes vibrational cooling on the 4–50 ps time scale. This is consistent with the absorption bands changes occurring over similar times in a recent femtosecond transient absorption study. We discuss a possible qualitative scenario for the formation of the iso-CH2I–I species that is in agreement with the available gas phase experimental results for the ultraviolet photodissociation reaction of diiodomethane and gas phase collisional deactivation studies of the CH2I radical. The proposed hypothesis is consistent with the lack of distinct resonance Raman bands in the first few picoseconds of our solution phase spectra of the iso-CH2I–I photoproduct as well as previously reported femtosecond transient absorption bands that are broad and weak in the 300–500 nm region over the 0.3–3 ps time scale. © 2000 American Institute of Physics.en_HK
dc.format.extent140563 bytes-
dc.format.extent25088 bytes-
dc.format.mimetypeapplication/pdf-
dc.format.mimetypeapplication/msword-
dc.languageengen_HK
dc.publisherAmerican Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jspen_HK
dc.rightsCreative Commons: Attribution 3.0 Hong Kong License-
dc.rightsCopyright (2000) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in (Journal Of Chemical Physics, 2000, v. 113 n. 17, p. 7471-7478) and may be found at (http://jcp.aip.org.eproxy2.lib.hku.hk/resource/1/jcpsa6/v113/i17/p7471_s1).-
dc.subjectPhysics chemistryen_HK
dc.titlePicosecond time-resolved resonance Raman observation of the iso-CH2I–I photoproduct from the 'photoisomerization' reaction of diiodomethane in the solution phaseen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0021-9606&volume=113&issue=17&spage=7471&epage=7478&date=2000&atitle=Picosecond+time-resolved+resonance+Raman+observation+of+the+iso-CH2I–I+photoproduct+from+the+%27photoisomerization%27+reaction+of+diiodomethane+in+the+solution+phaseen_HK
dc.identifier.emailLee Phillips, D:phillips@hku.hk-
dc.identifier.authorityLee Phillips, D=rp00770-
dc.description.naturepublished_or_final_versionen_HK
dc.identifier.doi10.1063/1.1313787en_HK
dc.identifier.scopuseid_2-s2.0-0034321076-
dc.identifier.hkuros62398-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0034321076&selection=ref&src=s&origin=recordpage-
dc.identifier.volume113-
dc.identifier.issue17-
dc.identifier.spage7471-
dc.identifier.epage7478-
dc.identifier.isiWOS:000090132900047-
dc.publisher.placeUnited States-
dc.identifier.scopusauthoridLee Phillips, D=7404519365-

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