Factors controlling the barriers to degenerate hydrogen atom transfers

Journal of the American Chemical Society

Volumn 127, Issue 16, 2005, Pages 5794-5795

  Isborn, Christine ^a   Hrovat, David A ^a,c   Borden, Weston Thatcher ^a,c   Mayer, James M ^a   Carpenter, Barry K ^b  

^a UNIVERSITY OF WASHINGTON   (United States)

^b Cornell University ^*  (United States)

^c UNIVERSITY OF NORTH TEXAS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CONFORMATIONAL TRANSITION; ENERGY TRANSFER; HYDROGEN ATOM TRANSFER;

AMMONIA; HYDROFLUORIC ACID; HYDROGEN; HYDROGEN PEROXIDE; HYDROXYLAMINE; KINETICS; METHANE; MODELS, MOLECULAR; THERMODYNAMICS; WATER;

EID: 17744371869     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja050024b     Document Type: Article

References (19)

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15. • + H-OH reactions. However, comparison with experiment apparently requires large tunneling corrections. See Supporting Information for references.
16. The procedure used here is quite similar in philosophy to that developed by Guthrie: Guthrie, J. P. ChemPhysChem 2003, 4, 809-816.
17. There is not a uniquely defined way to do this. We distorted X-H to its TS geometry by a pure stretching of the X-H bond.
18. 2ν TS (ΔH°), whereas CBS-QB3 puts it 1.29 kcal/mol above. The low symmetry makes geometry optimization at the UCCSD(T) level difficult. In any event, we judge the existence of this alternative TS to be irrelevant to the present discussion since it apparently depends on a hydrogen bond for its relative stability, and so would not be generally competitive.
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