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Article: Structural dynamics of 4-cyanobenzaldehyde in S2(ππ*) state

TitleStructural dynamics of 4-cyanobenzaldehyde in S2(ππ*) state
Authors
Issue Date2014
PublisherJohn Wiley & Sons Ltd. The Journal's web site is located at http://www3.interscience.wiley.com/cgi-bin/jhome/3420
Citation
Journal of Raman Spectroscopy, 2014, v. 45 n. 1, p. 105-113 How to Cite?
AbstractThe excited state structural dynamics of 4-cyanobenzaldehyde (p-CNB) were studied by using the resonance Raman spectroscopy and the quantum mechanical calculations. The experimental A- and B-band absorptions were, respectively, assigned to the major nO [RIGHTWARDS ARROW] π3* and π2 [RIGHTWARDS ARROW] π3* transitions according to the B3LYP-TD/6-31G(d) and CIS/6-31G(d) computations, and the resonance Raman spectra. It was determined that the actual S2(π2π3) state was in energy lower than S3(π1π3), which was just opposite to the B3LYP-TD/6-31G(d) calculated order of the S2(π1π3) and S3(π2π3). The vibrational assignments were carried out for the A- and B-band resonance Raman spectra. The B-band resonance Raman intensities of p-CNB were dominated by the C2–C3/C5–C6 symmetric stretch mode ν8, the overtones nν8 and their combination bands with the ring C–H bend mode ν17, the C9–N10 stretch mode ν6, the C7–O8 stretch mode ν7 and the remaining modes. The conical intersection between S1(nOπ3) and S2(π2π3) states of p-CNB was determined at complete active space self-consistent field (CASSCF)(8,7)/6-311G(d,p) level of theory. The B-band short-time structural dynamics and the corresponding decay dynamics of p-CNB were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. The resonance Raman spectra indicated that CI[S1(nOπ3)/S2(π1π2π3π4)] located nearby the Franck–Condon region. The excited state decay dynamics evolving from the S2, FC(π2π3) to the S1(nOπ3) state was proposed.
Persistent Identifierhttp://hdl.handle.net/10722/202568
ISSN
2015 Impact Factor: 2.395
2015 SCImago Journal Rankings: 1.075
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorYang, Yen_US
dc.contributor.authorPan, Sen_US
dc.contributor.authorXue, JDen_US
dc.contributor.authorZheng, Xen_US
dc.contributor.authorFang, WHen_US
dc.contributor.authorPhillips, DLen_US
dc.date.accessioned2014-09-19T08:41:21Z-
dc.date.available2014-09-19T08:41:21Z-
dc.date.issued2014en_US
dc.identifier.citationJournal of Raman Spectroscopy, 2014, v. 45 n. 1, p. 105-113en_US
dc.identifier.issn0377-0486en_US
dc.identifier.urihttp://hdl.handle.net/10722/202568-
dc.description.abstractThe excited state structural dynamics of 4-cyanobenzaldehyde (p-CNB) were studied by using the resonance Raman spectroscopy and the quantum mechanical calculations. The experimental A- and B-band absorptions were, respectively, assigned to the major nO [RIGHTWARDS ARROW] π3* and π2 [RIGHTWARDS ARROW] π3* transitions according to the B3LYP-TD/6-31G(d) and CIS/6-31G(d) computations, and the resonance Raman spectra. It was determined that the actual S2(π2π3) state was in energy lower than S3(π1π3), which was just opposite to the B3LYP-TD/6-31G(d) calculated order of the S2(π1π3) and S3(π2π3). The vibrational assignments were carried out for the A- and B-band resonance Raman spectra. The B-band resonance Raman intensities of p-CNB were dominated by the C2–C3/C5–C6 symmetric stretch mode ν8, the overtones nν8 and their combination bands with the ring C–H bend mode ν17, the C9–N10 stretch mode ν6, the C7–O8 stretch mode ν7 and the remaining modes. The conical intersection between S1(nOπ3) and S2(π2π3) states of p-CNB was determined at complete active space self-consistent field (CASSCF)(8,7)/6-311G(d,p) level of theory. The B-band short-time structural dynamics and the corresponding decay dynamics of p-CNB were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. The resonance Raman spectra indicated that CI[S1(nOπ3)/S2(π1π2π3π4)] located nearby the Franck–Condon region. The excited state decay dynamics evolving from the S2, FC(π2π3) to the S1(nOπ3) state was proposed.en_US
dc.languageengen_US
dc.publisherJohn Wiley & Sons Ltd. The Journal's web site is located at http://www3.interscience.wiley.com/cgi-bin/jhome/3420en_US
dc.relation.ispartofJournal of Raman Spectroscopyen_US
dc.rightsJournal of Raman Spectroscopy. Copyright © John Wiley & Sons Ltd.en_US
dc.titleStructural dynamics of 4-cyanobenzaldehyde in S2(ππ*) stateen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL: phillips@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.description.naturelink_to_OA_fulltext-
dc.identifier.doi10.1002/jrs.4420en_US
dc.identifier.scopuseid_2-s2.0-84892514450-
dc.identifier.hkuros237017en_US
dc.identifier.volume45en_US
dc.identifier.issue1en_US
dc.identifier.spage105en_US
dc.identifier.epage113en_US
dc.identifier.isiWOS:000329687100015-
dc.publisher.placeUnited Kingdomen_US

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