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15944396222
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note
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12 show that a bending mode does not significantly alter the adiabatic PT picture, especially the KIE.
-
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-
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68
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15944363899
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note
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bT/h.
-
-
-
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69
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15944399851
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-
note
-
o is not expected to be exactly 0.5 due to "intrinsic" asymmetry, but the deviation from 0.5 for either H or D is not expected to be significant (cf. ref 42 in ref 7a). Also, the present analysis assumes that the underlying electronic structure variation with PT should be approximately describable with two dominant VB structures. This is unlikely to apply to certain PT reactions, most notably those involving carbon acids (cf. ref 42 in ref 7b).
-
-
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70
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15944380532
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note
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The precise connection with the activation energy in an Arrhenius plot will be taken up in Section 3.
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71
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15944398807
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note
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A further potential source of temperature dependence could involve differential thermal populations, at the TS and at R, of the proton and H-bond vibrations. Since we are only including the ground vibrational levels of these modes in the present study, there is no such contribution.
-
-
-
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76
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15944408973
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note
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The literature concerning this solvent coordinate for both PT and ET is quite extensive. For examples, see references in ref 7.
-
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77
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15944362686
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note
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6a
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78
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15944363202
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note
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-1. The full PT rate with H-bond motion includes excitations of the Q mode. Since the H-bond frequency is larger near the TS than in the reactant, the reaction barrier increases with excitation in Q, and thus, the reaction is dominated by the ground Q vibrational state PT rate. See Section 2b in ref 7b for further details.
-
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79
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15944386106
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note
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R and k‡.
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o).
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15944389094
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note
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o variation.
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87
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0001189810
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This behavior parallels the temperature dependence of the reorganization energy for electron transfer reactions. See, e.g., Vath, P.; Zimmt, M.B. J. Phys. Chem. A 2000, 104, 2626-2633.
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