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Water Catalysis and Anticatalysis in Photochemical Reactions: Observation of a Delayed Threshold Effect in the Reaction Quantum Yield
Kramer, Zeb C.1,2; Takahashi, Kaito1; Skodje, Rex T.1,2
Source PublicationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2010-11-03
DOI10.1021/ja107335t
Volume132Issue:43Pages:15154-15157
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Multidisciplinary
WOS Research AreaChemistry
WOS KeywordGAS-PHASE REACTION ; MOLECULAR-ORBITAL METHODS ; DIELS-ALDER REACTIONS ; BASIS-SETS ; ELIMINATION-REACTIONS ; ORGANIC-REACTIONS ; TRANSITION-STATE ; DYNAMICS ; MECHANISM ; HYDRATION
AbstractThe possible catalysis of photochemical reactions by water molecules is considered. Using theoretical simulations, we investigate the HF-elimination reaction of fluoromethanol in small water clusters initiated by the overtone excitation of the hydroxyl group. The reaction occurs in competition with the process of water evaporation that dissipates the excitation and quenches the reaction. Although the transition state barrier is stabilized by over 20 kcal/mol through hydrogen bonding with water, the quantum yield versus energy shows a pronounced delayed threshold that effectively eliminates the catalytic effect. It is concluded that the quantum chemistry calculations of barrier lowering are not sufficient to infer water catalysis in some photochemical reactions, which instead require dynamical modeling.
Language英语
WOS IDWOS:000283621700019
Citation statistics
Cited Times:13[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/141849
Collection中国科学院大连化学物理研究所
Affiliation1.Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA
2.CAS, Dalian Inst Chem Phys, Key State Lab Mol React Dynam, Dalian, Peoples R China
Recommended Citation
GB/T 7714
Kramer, Zeb C.,Takahashi, Kaito,Skodje, Rex T.. Water Catalysis and Anticatalysis in Photochemical Reactions: Observation of a Delayed Threshold Effect in the Reaction Quantum Yield[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2010,132(43):15154-15157.
APA Kramer, Zeb C.,Takahashi, Kaito,&Skodje, Rex T..(2010).Water Catalysis and Anticatalysis in Photochemical Reactions: Observation of a Delayed Threshold Effect in the Reaction Quantum Yield.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,132(43),15154-15157.
MLA Kramer, Zeb C.,et al."Water Catalysis and Anticatalysis in Photochemical Reactions: Observation of a Delayed Threshold Effect in the Reaction Quantum Yield".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 132.43(2010):15154-15157.
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