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Volumn 44, Issue 1-3, 2004, Pages 171-184

Temperature-dependent solvent polarity effects on adiabatic proton transfer rate constants and kinetic isotope effects

Author keywords

[No Author keywords available]

Indexed keywords

ISOTOPE;

EID: 11344288882     PISSN: 00212148     EISSN: None     Source Type: Journal    
DOI: 10.1560/K3BH-D2K9-PDU9-NA80     Document Type: Conference Paper
Times cited : (18)

References (91)
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    • Kinetic Isotope Effects for Nonadiabatic Proton Transfer Reactions in a Polar Environment I. Isotopic Identification of Tunneling
    • Submitted to
    • (a) Kiefer, P.M.; Hynes, J.T. Kinetic Isotope Effects for Nonadiabatic Proton Transfer Reactions in a Polar Environment I. Isotopic Identification of Tunneling. Submitted to J. Phys. Chem. A.
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    • (b) Kiefer, P.M.; Hynes, J.T. Kinetic Isotope Effects for Nonadiabatic Proton Transfer Reactions in a Polar Environment II. Comparison with Electronically Diabatic Descriptions. Submitted to J. Phys. Chem. A.
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    • A temperature-dependent analysis, involving solvent dynamics, of an excited electronic state proton transfer (interpreted, however, as being nonadiabatic tunneling PT and employing an analysis similar to that of ref 14a) is given in Poles, E.; Cohen, B.; Huppert, D. Isr. J. Chem. 1999, 39, 347-360.
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    • For examples of PT in complex systems where the proton is explicitly included in the reaction coordinate, see (a) Bash, P.A.; Field, M.J.; Davenport, R.C.; Petsko, G.A.; Ringe, D.; Karplus, M. Biochemistry 1991, 30, 5826-5832. (b) Cui, Q.; Karplus, M. J. Am. Chem. Soc. 2001, 123, 2284-2290. (c) Alhambra, C.; Corchado, J.; Sánchez, M.L.; Garcia-Viloca, M.; Gao, J.; Truhlar, D.G. J. Phys. Chem. B 2001, 105, 11326-11340. (d) Cui, Q.; Elstner, M.; Karplus, M. J. Phys. Chem. B 2002, 106, 2721-2740.
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    • For examples of PT in complex systems where the proton is explicitly included in the reaction coordinate, see (a) Bash, P.A.; Field, M.J.; Davenport, R.C.; Petsko, G.A.; Ringe, D.; Karplus, M. Biochemistry 1991, 30, 5826-5832. (b) Cui, Q.; Karplus, M. J. Am. Chem. Soc. 2001, 123, 2284-2290. (c) Alhambra, C.; Corchado, J.; Sánchez, M.L.; Garcia-Viloca, M.; Gao, J.; Truhlar, D.G. J. Phys. Chem. B 2001, 105, 11326-11340. (d) Cui, Q.; Elstner, M.; Karplus, M. J. Phys. Chem. B 2002, 106, 2721-2740.
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 2284-2290
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    • For examples of PT in complex systems where the proton is explicitly included in the reaction coordinate, see (a) Bash, P.A.; Field, M.J.; Davenport, R.C.; Petsko, G.A.; Ringe, D.; Karplus, M. Biochemistry 1991, 30, 5826-5832. (b) Cui, Q.; Karplus, M. J. Am. Chem. Soc. 2001, 123, 2284-2290. (c) Alhambra, C.; Corchado, J.; Sánchez, M.L.; Garcia-Viloca, M.; Gao, J.; Truhlar, D.G. J. Phys. Chem. B 2001, 105, 11326-11340. (d) Cui, Q.; Elstner, M.; Karplus, M. J. Phys. Chem. B 2002, 106, 2721-2740.
    • (2001) J. Phys. Chem. B , vol.105 , pp. 11326-11340
    • Alhambra, C.1    Corchado, J.2    Sánchez, M.L.3    Garcia-Viloca, M.4    Gao, J.5    Truhlar, D.G.6
  • 66
    • 0037076062 scopus 로고    scopus 로고
    • For examples of PT in complex systems where the proton is explicitly included in the reaction coordinate, see (a) Bash, P.A.; Field, M.J.; Davenport, R.C.; Petsko, G.A.; Ringe, D.; Karplus, M. Biochemistry 1991, 30, 5826-5832. (b) Cui, Q.; Karplus, M. J. Am. Chem. Soc. 2001, 123, 2284-2290. (c) Alhambra, C.; Corchado, J.; Sánchez, M.L.; Garcia-Viloca, M.; Gao, J.; Truhlar, D.G. J. Phys. Chem. B 2001, 105, 11326-11340. (d) Cui, Q.; Elstner, M.; Karplus, M. J. Phys. Chem. B 2002, 106, 2721-2740.
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    • Cui, Q.1    Elstner, M.2    Karplus, M.3
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    • note
    • 12 show that a bending mode does not significantly alter the adiabatic PT picture, especially the KIE.
  • 68
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    • note
    • bT/h.
  • 69
    • 15944399851 scopus 로고    scopus 로고
    • 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).
  • 70
    • 15944380532 scopus 로고    scopus 로고
    • note
    • The precise connection with the activation energy in an Arrhenius plot will be taken up in Section 3.
  • 71
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    • note
    • 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.
  • 76
    • 15944408973 scopus 로고    scopus 로고
    • note
    • The literature concerning this solvent coordinate for both PT and ET is quite extensive. For examples, see references in ref 7.
  • 77
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    • note
    • 6a
  • 78
    • 15944363202 scopus 로고    scopus 로고
    • note
    • -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.
  • 79
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    • note
    • R and k‡.
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    • (b) Cleland, W.W.; Frey, P.A.; Gerlt, J.A. J. Biol. Chem. 1998, 273, 25529-25532. We stress that in adiabatic PT, the "low barrier H-bond" situation occurs at an activated TS configuration in the solvent coordinate (see middle panel of Fig. 2a).
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    • A comparison between a microscopic description and a dielectric continuum description (where the effect is governed by the T derivative of the dielectric constant, as in eq 30) is given in Morita, T.; Ladanyi, B.M.; Hynes, J.T. J. Phys. Chem. 1989, 93, 1386-1392.
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    • Morita, T.1    Ladanyi, B.M.2    Hynes, J.T.3
  • 85
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    • note
    • o).
  • 86
    • 15944389094 scopus 로고    scopus 로고
    • note
    • o variation.
  • 87
    • 0001189810 scopus 로고    scopus 로고
    • 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.
    • (2000) J. Phys. Chem. A , vol.104 , pp. 2626-2633
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.