File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Photochemistry of butyrophenone: Combined complete-active-space self-consistent field and density functional theory study of norrish type I and II reactions

TitlePhotochemistry of butyrophenone: Combined complete-active-space self-consistent field and density functional theory study of norrish type I and II reactions
Authors
Issue Date2004
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpca
Citation
Journal Of Physical Chemistry A, 2004, v. 108 n. 25, p. 5386-5392 How to Cite?
AbstractThe complete-active-space self-consistent field (CASSCF) and density functional theory (DFT) approaches V have been used to study the mechanistic details of Norrish type I and II reactions of aromatic carbonyl compounds, with butyrophenone (PhCOCH 2CH 2CH 3) as a representative. A minimum energy crossing point was found to exist among three potential energy surfaces (S 1, T 1, and T 2), and the three-surface crossing allows the T 2 state to act as a relay that enables the intersystem crossing (ISC) from S 1 to T 1 to occur with a high efficiency for PhCOCH 2CH 2CH 3. Once the molecule is in the T 1 state, the 1,5-H shift reaction is the predominant reaction pathway and yields a triplet 1,4-biradical of PhC(OH)CH 2CH 2CH 2 as an intermediate species. Since the formation of excited triplet products is energetically improbable, the subsequent decomposition, cyclicization, and disproportionation of the 1,4-biradical proceed after intersystem crossing from the triplet to singlet state. The singlet 1,4-biradical was found to have three isomers, which determine to a certain extent the branching ratios of the subsequent reactions. The study given here provides new insights into the Si relaxation dynamics of aromatic carbonyl compounds and their subsequent reaction mechanisms.
Persistent Identifierhttp://hdl.handle.net/10722/70058
ISSN
2015 Impact Factor: 2.883
2015 SCImago Journal Rankings: 1.231
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorHe, HYen_HK
dc.contributor.authorFang, WHen_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2010-09-06T06:19:19Z-
dc.date.available2010-09-06T06:19:19Z-
dc.date.issued2004en_HK
dc.identifier.citationJournal Of Physical Chemistry A, 2004, v. 108 n. 25, p. 5386-5392en_HK
dc.identifier.issn1089-5639en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70058-
dc.description.abstractThe complete-active-space self-consistent field (CASSCF) and density functional theory (DFT) approaches V have been used to study the mechanistic details of Norrish type I and II reactions of aromatic carbonyl compounds, with butyrophenone (PhCOCH 2CH 2CH 3) as a representative. A minimum energy crossing point was found to exist among three potential energy surfaces (S 1, T 1, and T 2), and the three-surface crossing allows the T 2 state to act as a relay that enables the intersystem crossing (ISC) from S 1 to T 1 to occur with a high efficiency for PhCOCH 2CH 2CH 3. Once the molecule is in the T 1 state, the 1,5-H shift reaction is the predominant reaction pathway and yields a triplet 1,4-biradical of PhC(OH)CH 2CH 2CH 2 as an intermediate species. Since the formation of excited triplet products is energetically improbable, the subsequent decomposition, cyclicization, and disproportionation of the 1,4-biradical proceed after intersystem crossing from the triplet to singlet state. The singlet 1,4-biradical was found to have three isomers, which determine to a certain extent the branching ratios of the subsequent reactions. The study given here provides new insights into the Si relaxation dynamics of aromatic carbonyl compounds and their subsequent reaction mechanisms.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpcaen_HK
dc.relation.ispartofJournal of Physical Chemistry Aen_HK
dc.titlePhotochemistry of butyrophenone: Combined complete-active-space self-consistent field and density functional theory study of norrish type I and II reactionsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1089-5639&volume=108&issue=25&spage=5386&epage=5392&date=2004&atitle=Photochemistry+of+butyrophenone:+combined+complete-active-space+self-consistent+field+and+density+functional+theory+study+of+norrish+type+I+and+II+reactionsen_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jp037735len_HK
dc.identifier.scopuseid_2-s2.0-3142745324en_HK
dc.identifier.hkuros99136en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-3142745324&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume108en_HK
dc.identifier.issue25en_HK
dc.identifier.spage5386en_HK
dc.identifier.epage5392en_HK
dc.identifier.isiWOS:000222125800011-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridHe, HY=55214939300en_HK
dc.identifier.scopusauthoridFang, WH=7202236871en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats