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Volumn 102, Issue 21, 1998, Pages 3648-3658

Direct dynamics quasiclassical trajectory study of the thermal stereomutations of cyclopropane

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EID: 0347482791     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp973273y     Document Type: Article
Times cited : (85)

References (105)
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    • note
    • 1 on the isotope effect.
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    • note
    • 1′.
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    • Hase, W. L.; Duchovic, R. J.; Hu, X.; Komornicki, A.; Lim, K.; Lu, D.-h.; Peslherbe, G. H.; Swamy, K. N.; Vande Linde, S. R.; Wang, H.; Wolfe, R. J. VENUS 96, a General Chemical Dynamics Computer Program. QCPE 1996, 16, 671. VENUS 96 is an enhanced version of MERCURY: Hase. W. L. QCPE 1983, 3, 453.
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    • Variational TST calculations using MOPAC with specific reaction path parameters have been reported in the following, (a) Gonzalez-Lafont, A.; Truong, T. N.; Truhlar, D. G. J. Phys. Chem. 1991, 95, 4618. (b) Liu, Y.-P.; Lu, D.-H.; Gonzalez-Lafont, A.; Truhlar, D. G.; Garrett, B. C. J. Am. Chem. Soc. 1993, 115, 7806.
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    • Variational TST calculations using MOPAC with specific reaction path parameters have been reported in the following, (a) Gonzalez-Lafont, A.; Truong, T. N.; Truhlar, D. G. J. Phys. Chem. 1991, 95, 4618. (b) Liu, Y.-P.; Lu, D.-H.; Gonzalez-Lafont, A.; Truhlar, D. G.; Garrett, B. C. J. Am. Chem. Soc. 1993, 115, 7806.
    • (1993) J. Am. Chem. Soc. , vol.115 , pp. 7806
    • Liu, Y.-P.1    Lu, D.-H.2    Gonzalez-Lafont, A.3    Truhlar, D.G.4    Garrett, B.C.5
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    • To be published, quoted in ref 4c. The preliminary value in ref 8 was 120 ± 20 fs
    • Herek, J. L.; Zewail, A. H. To be published, quoted in ref 4c. The preliminary value in ref 8 was 120 ± 20 fs.
    • Herek, J.L.1    Zewail, A.H.2
  • 84
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    • note
    • ‡, and CT‡ imply nearly identical torsional partition functions for a given deuteration pattern. Conventional rather than variational TST is assumed.
  • 96
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    • note
    • -1; above 1200 the variation rapidly decreases.
  • 98
    • 85034293357 scopus 로고    scopus 로고
    • note
    • Each methylene was rotated rigidly as a unit about the C-C bond during the sampling. Only the hydrogens were rotated, and all other internal coordinates were held fixed.
  • 101
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    • note
    • C.D. is grateful to the Cornell Theory Center for a grant of computer time.
  • 102
    • 85034302296 scopus 로고    scopus 로고
    • note
    • ‡; ref 34 has the correct ordering. (2) Reference 34 does not allow propene formation; AM1-SRP includes it.(3) In AM1-SRP, Dis‡ is a second-order saddle point; in ref 34 CT‡ is a second-order saddle point. On the ab initio PES both are first-order saddle points.
  • 105
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    • note
    • The TS criterion CCC = 94° was determined in ref 24a by Monte Carlo calculation of the relative sum of states as a function of geometry projected onto the CCC angle. However, this TS criterion was not used in the present calculations because nearly all trajectories initiated at CCC = 94° cyclize immediately without isomerization. This shows that the use of CCC = 94° as the sole TS criterion is not adequate at 695 K and suggests that the TS definition should include a larger number of coordinates and perhaps momenta as well.


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