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题名: Internal Conversion versus Intersystem Crossing: What Drives the Gas Phase Dynamics of Cyclic alpha,beta-Enones?
作者: Schalk, Oliver1, 2, 3;  Schuurman, Michael S.3;  Wu, Guorong3, 4, 5;  Lang, Peter2;  Mucke, Melanie6;  Feifel, Raimund6;  Stolow, Albert3
刊名: JOURNAL OF PHYSICAL CHEMISTRY A
发表日期: 2014-03-27
DOI: 10.1021/jp4124937
卷: 118, 期:12, 页:2279-2287
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Chemistry ;  Physics
英文摘要: We investigate the competition between intersystem crossing (ISC) and internal conversion (IC) as nonradiative relaxation pathways in cyclic alpha,beta-unsaturated enones following excitation to their lowest lying (1)pi pi* state, by means of time-resolved photoelectron spectroscopy and ab initio computation. Upon excitation, the (1)pi pi* state of 2-cyclopentenone decays to the lowest lying (1)pi pi* state within 120 +/- 20 fs. Within 1.2 +/- 0.2 ps, the molecule subsequently decays to the triplet manifold and the singlet ground state, with quantum yields of 0.35 and 0.65, respectively. The corresponding dynamics in modified derivatives, obtained by selective methylation, show a decrease in both IC and ISC rates, with the quantum yields of ISC varying between 0.35 and 0.08. The rapid rates of ISC are explained by a large spin orbit coupling of 45-60 cm(-1) over an extended region of near degeneracy between the singlet and triplet state. Furthermore, the rate of IC is depressed by the existence of a well-defined minimum on the (1)n pi* potential energy surface. The nonadiabatic pathways evinced by the present results highlight the fact that these molecular systems conceptually represent "intermediate cases" between ultrafast dynamics mediated by vibrational motions at conical intersections versus those by statistical decay mechanisms.
关键词[WOS]: RESOLVED PHOTOELECTRON-SPECTROSCOPY ;  193 NM ;  CONICAL INTERSECTIONS ;  EXCITED-STATE ;  NONADIABATIC DYNAMICS ;  ACROLEIN ;  TRIPLET ;  PHOTOCHEMISTRY ;  PHOTODISSOCIATION ;  MOLECULES
语种: 英语
WOS记录号: WOS:000333578100012
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/145483
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Stockholm Univ, Alba Nova Univ Ctr, Dept Phys, S-10961 Stockholm, Sweden
2.Univ Munich, Lehrstuhl BioMol Opt, D-80538 Munich, Germany
3.Natl Res Council Canada, Ottawa, ON K1A 0R6, Canada
4.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China
5.Univ Sci & Technol China, Synerget Innovat Ctr Quantum Informat & Quantum P, Hefei 230026, Anhui, Peoples R China
6.Uppsala Univ, Dept Phys & Astron, S-75120 Uppsala, Sweden

Recommended Citation:
Schalk, Oliver,Schuurman, Michael S.,Wu, Guorong,et al. Internal Conversion versus Intersystem Crossing: What Drives the Gas Phase Dynamics of Cyclic alpha,beta-Enones?[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2014,118(12):2279-2287.
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