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A recent review of PCET is given in: Mayer, J. M. Annu. Rev. Phys. Chem. 2004, 55, 363-390.
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6 have argued that a rigorous distinction between the two mechanisms is not possible because the proton and electron behave quantum mechanically.
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6 have argued that a rigorous distinction between the two mechanisms is not possible because the proton and electron behave quantum mechanically.
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33846047459
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For solution- or gas-phase processes. It is likely that some PCET reactions in an enzyme environment do not require the formation of a H-bond. See
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For solution- or gas-phase processes. It is likely that some PCET reactions in an enzyme environment do not require the formation of a H-bond. See: Hatcher, E.; Soudackov, A. V.; Hammes-Schiffer, S. J. Am. Chem. Soc. 2007, 129, 187-196.
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Frisch, M. J.; et al. Gaussian 03, revision D.01; Gaussian, Inc.: Wallingford, CT, 2004.
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Laidler, K. J. Chemical Kinetics, 3rd ed.; Harper and Row: New York, 1987.
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Laidler, K.J.1
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Werner, H.-J.; et al. MOLPRO, version 2002.1, a package of ab initio programs; 2002 (http://www.molpro.net).
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20
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34249018129
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2 groups in the iminoxyl/oxime transition state associated with the reaction illustrated in Figure 1b are 0.05 (HOMO-2) and -0.15 (SOMO), with the negative value indicating an antibonding interaction.
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2 groups in the iminoxyl/oxime transition state associated with the reaction illustrated in Figure 1b are 0.05 (HOMO-2) and -0.15 (SOMO), with the negative value indicating an antibonding interaction.
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21
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0004107550
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For an overlap analysis for the water molecule, see:, 4th ed, Prentice Hall: Englewood Cliffs, NJ
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For an overlap analysis for the water molecule, see: Levine, I. N. Quantum Chemistry, 4th ed.; Prentice Hall: Englewood Cliffs, NJ, 1991.
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Quantum Chemistry
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Levine, I.N.1
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22
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14644439850
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Computational studies of the hydroperoxyl/phenol couple found the reaction to occur via a PCET process: Singh, N, O'Malley, P. J, Popelier, P. L. A. Phys. Chem. Chem. Phys. 2005, 7, 614-619
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Computational studies of the hydroperoxyl/phenol couple found the reaction to occur via a PCET process: Singh, N.; O'Malley, P. J.; Popelier, P. L. A. Phys. Chem. Chem. Phys. 2005, 7, 614-619.
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24
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2442711469
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• is a strong electron-withrdrawing group. See: Pratt, D. A.; DiLabio, G. A.; Mulder, P.; Ingold, K. U. Acc. Chem. Res. 2004, 37, 334-340.
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• is a strong electron-withrdrawing group. See: Pratt, D. A.; DiLabio, G. A.; Mulder, P.; Ingold, K. U. Acc. Chem. Res. 2004, 37, 334-340.
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25
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34249110479
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Recent work by Lingwood et al.23 showed that the MPW1K 24 method predicts accurate rate constants and barrier heights for certain PCET reactions. For the tert-butylperoxyl/phenol couple, MPW1K predicts kCTST, 4.9 × 10-3 M-1 s-1 and Ea, 13.1 kcal/mol relative to separated reactants, The latter value is in very poor agreement with the experimental Ea, despite the fact that the method was specifically parameterized for hydrogen atom transfer reactions. We attribute this large error to a poor description of the charge separation in the PCET transition state
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a, despite the fact that the method was specifically parameterized for hydrogen atom transfer reactions. We attribute this large error to a poor description of the charge separation in the PCET transition state.
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26
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2 structure.
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2 structure.
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39
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2h structure.
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2h structure.
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40
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Bally, T.1
Borden, W.T.2
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34249107842
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We also performed calculations with dispersion-corrected B3LYP. A rigid potential energy scan about the CC-[H]-CC dihedral was performed with B3LYP/6-311++G(2d,2p) in 5° increments, starting at the optimized C2h geometry. The dispersion energy was obtained at each point on the potential energy surface using the method of Johnson and Becke35 with parameters a1, 0.52 and a 2, 1.98 Å. These new parameter values were determined by minimizing the root-mean-square percent error in the binding energies of a test set of seven dispersion-bound hydrocarbon complexes methane dimer, methane-ethylene, ethylene dimer, methane-benzene, and the parallel, T-shaped, and slipped-parallel conformations of the benzene dimer, This gave an optimum dihedral of ca. 40°, in good agreement with the MP2 results
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2 = 1.98 Å. These new parameter values were determined by minimizing the root-mean-square percent error in the binding energies of a test set of seven dispersion-bound hydrocarbon complexes (methane dimer, methane-ethylene, ethylene dimer, methane-benzene, and the parallel, T-shaped, and slipped-parallel conformations of the benzene dimer). This gave an optimum dihedral of ca. 40°, in good agreement with the MP2 results.
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