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Article: Picosecond Time-Resolved Study of 4-Dimethylaminobenzonitrile in Polar and Nonpolar Solvents

TitlePicosecond Time-Resolved Study of 4-Dimethylaminobenzonitrile in Polar and Nonpolar Solvents
Authors
Issue Date2000
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpca
Citation
Journal Of Physical Chemistry A, 2000, v. 104 n. 18, p. 4188-4197 How to Cite?
AbstractBy applying a Kerr gate to reject fluorescence, the picosecond time-resolved resonance Raman (TR 3) spectrum of the intramolecular charge-transfer (ICT) state of 4-dimethylaminobenzonitrile (DMABN) in a polar solvent has been obtained for the first time. To elucidate the geometric and electronic structural changes occurring in DMABN in different solvent environments following electronic excitation, the same method (without the Kerr gate) was also used to study the delocalized excited (DE) state of DMABN. The TR 3 spectrum of the ICT state is dominated by a phenyl ring band, while the band corresponding to the C≡N stretching mode is absent. The TR 3 spectrum of the DE state, observed in nonpolar solvents, implies a planar structure with double bond character in the C ring-N(CH 3) 2 bond. Conjugation therefore extends mainly between the dimethylamino group and the ring in the DE state. The Kerr gate has also been used to measure the temporal spectral profile of the DMABN fluorescence in both nonpolar and polar solutions with 3 ps time resolution covering the spectral window from 320 to 560 nm. Subpicosecond transient absorption spectra of DMABN in solvents of different polarity have also been measured. The presence of an isosbestic point in the time-resolved fluorescence spectra at early time delays demonstrates the interchange of a two-state system during the initial relaxation process following the photoexcitation. The results are discussed and placed in context with the wealth of work performed to date on this molecular system.
Persistent Identifierhttp://hdl.handle.net/10722/167348
ISSN
2015 Impact Factor: 2.883
2015 SCImago Journal Rankings: 1.231
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorKwok, WMen_US
dc.contributor.authorMa, Cen_US
dc.contributor.authorPhillips, Den_US
dc.contributor.authorMatousek, Pen_US
dc.contributor.authorParker, AWen_US
dc.contributor.authorTowrie, Men_US
dc.date.accessioned2012-10-08T03:05:55Z-
dc.date.available2012-10-08T03:05:55Z-
dc.date.issued2000en_US
dc.identifier.citationJournal Of Physical Chemistry A, 2000, v. 104 n. 18, p. 4188-4197en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/10722/167348-
dc.description.abstractBy applying a Kerr gate to reject fluorescence, the picosecond time-resolved resonance Raman (TR 3) spectrum of the intramolecular charge-transfer (ICT) state of 4-dimethylaminobenzonitrile (DMABN) in a polar solvent has been obtained for the first time. To elucidate the geometric and electronic structural changes occurring in DMABN in different solvent environments following electronic excitation, the same method (without the Kerr gate) was also used to study the delocalized excited (DE) state of DMABN. The TR 3 spectrum of the ICT state is dominated by a phenyl ring band, while the band corresponding to the C≡N stretching mode is absent. The TR 3 spectrum of the DE state, observed in nonpolar solvents, implies a planar structure with double bond character in the C ring-N(CH 3) 2 bond. Conjugation therefore extends mainly between the dimethylamino group and the ring in the DE state. The Kerr gate has also been used to measure the temporal spectral profile of the DMABN fluorescence in both nonpolar and polar solutions with 3 ps time resolution covering the spectral window from 320 to 560 nm. Subpicosecond transient absorption spectra of DMABN in solvents of different polarity have also been measured. The presence of an isosbestic point in the time-resolved fluorescence spectra at early time delays demonstrates the interchange of a two-state system during the initial relaxation process following the photoexcitation. The results are discussed and placed in context with the wealth of work performed to date on this molecular system.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpcaen_US
dc.relation.ispartofJournal of Physical Chemistry Aen_US
dc.titlePicosecond Time-Resolved Study of 4-Dimethylaminobenzonitrile in Polar and Nonpolar Solventsen_US
dc.typeArticleen_US
dc.identifier.emailMa, C:macs@hkucc.hku.hken_US
dc.identifier.authorityMa, C=rp00758en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jp9927606-
dc.identifier.scopuseid_2-s2.0-0001482495en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0001482495&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume104en_US
dc.identifier.issue18en_US
dc.identifier.spage4188en_US
dc.identifier.epage4197en_US
dc.identifier.isiWOS:000087003100009-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridKwok, WM=7103129332en_US
dc.identifier.scopusauthoridMa, C=7402924979en_US
dc.identifier.scopusauthoridPhillips, D=22998496000en_US
dc.identifier.scopusauthoridMatousek, P=7005659005en_US
dc.identifier.scopusauthoridParker, AW=7403267977en_US
dc.identifier.scopusauthoridTowrie, M=7004415080en_US

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