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To be published, quoted in ref 4c. The preliminary value in ref 8 was 120 ± 20 fs
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‡, and CT‡ imply nearly identical torsional partition functions for a given deuteration pattern. Conventional rather than variational TST is assumed.
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85034285010
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note
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-
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98
-
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85034293357
-
-
note
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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.
-
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-
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101
-
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85034283988
-
-
note
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C.D. is grateful to the Cornell Theory Center for a grant of computer time.
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102
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85034302296
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note
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‡; 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.
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103
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36449000211
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(a) Schranz, H. W.; Raff, L. M.; Thompson, D. L. J. Chem. Phys. 1991, 94, 4219-4229.
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(1991)
J. Chem. Phys.
, vol.94
, pp. 4219-4229
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Schranz, H.W.1
Raff, L.M.2
Thompson, D.L.3
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104
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0006785735
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(b) Sewell, T. D.; Schranz, H. W.; Raff, L. M.; Thompson, D. L. J. Chem. Phys. 1991, 95, 8089.
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(1991)
J. Chem. Phys.
, vol.95
, pp. 8089
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Sewell, T.D.1
Schranz, H.W.2
Raff, L.M.3
Thompson, D.L.4
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105
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85034282377
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note
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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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