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Volumn 121, Issue 48, 1999, Pages 11171-11178

Application of trajectory surface hopping to the study of a symmetry- forbidden intramolecular hole transfer process in bismethyleneadamantane cation radical

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE;

EID: 0033537038     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9917823     Document Type: Article
Times cited : (25)

References (70)
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    • Bolton, J. R., Mataga, N., McLendon, G. L., Eds ; Advances in Chemistry Series 228; American Chemical Society: Washington, DC, Chapter 2
    • (a) Bolton, J. R.; Archer, M. D. In Electron Transfer in Inorganic, Organic and Biological Systems; Bolton, J. R., Mataga, N., McLendon, G. L., Eds ; Advances in Chemistry Series 228; American Chemical Society: Washington, DC, 1991; Chapter 2, pp 7-23.
    • (1991) Electron Transfer in Inorganic, Organic and Biological Systems , pp. 7-23
    • Bolton, J.R.1    Archer, M.D.2
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    • Part B; Miller, W. H., Ed.; Plenum: New York
    • (f) Tully, J. C. In Dynamics of Molecular Collisions. Part B; Miller, W. H., Ed.; Plenum: New York, 1976; p 217.
    • (1976) Dynamics of Molecular Collisions , pp. 217
    • Tully, J.C.1
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    • Allen, M. P., Tildesley, D. J., Eds.; Kluwer Academic Publishers: Dordrecht
    • (c) Coker, D. F. In Computer Simulation in Chemical Physics; Allen, M. P., Tildesley, D. J., Eds.; Kluwer Academic Publishers: Dordrecht, 1993; Vol. 397.
    • (1993) Computer Simulation in Chemical Physics , vol.397
    • Coker, D.F.1
  • 66
    • 84920346871 scopus 로고    scopus 로고
    • note
    • While it is tempting to equate the reciprocal of our τ values to the corresponding unimolecular rate constants for HT, it is strictly incorrect to do so because the trajectories are halted immediately following HT, without allowing them the opportunity to recross from product well into reactant well. That is, we are assuming infinitely fast deactivation in the product well, whereas dissipation in the reactant well occurs only through dynamics of the atoms. The reciprocal of our τ values would be equal to the unimolecular rate constant in the high-pressure limit (i.e. in solution) if intramolecular vibrational energy redistribution were very much faster than passage over the reaction barrier, but we have no information about that. We are grateful to a referee and to Professor D. G. Truhlar for helpful comments on this point.
  • 67
    • 84920350628 scopus 로고    scopus 로고
    • note
    • F-tests performed to compare the relative qualities of the monoexponential and biexponential fits to the decay data for 4b revealed that the biexponential fit is in fact significantly better at the 95% confidence limit.
  • 70
    • 84920355472 scopus 로고    scopus 로고
    • note
    • Although the decay data for 4b are expressed more precisely by a biexponential function, the kinetic isotope effect for HT between 4a and 4b is calculated by using the rate constant obtained from the monoexponential fit to the decay data for 4b. Errors introduced by using this fit are assumed to be small.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.