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A fragment of 22 sites was considered with G at site one, GGG at site N + 2, and A at the remaining sites.
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The range for the couplings obtained in ref 45 is due to slightly different equilibrium geometries for different systems with available crystallographic data.
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AG = 0.14 eV, is smaller than the values of 0.2, 0.47, and 0.46 eV resulting grom gas-phase measurements, measurements in solution, and semiempirical calculations that were discussed in detail in Appendix F. One should note, however, that the energetic difference between G and the partially delocalized bridge states of A's is larger than this value because of the different solvation energies of the localized state at G and the partially delocalized bridge states.
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53
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0242377720
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note
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The present energetic gap between G and GGG to 0.2 eV may be compared with a wide variety of other values, such as the 0.68 eV estimated from earlier ab initio calculations (Sugiyama, H.; Saito, I. J. Am. Chem. Soc. 1996, 118, 7063) and of 0.13 eV estimated in recent semiempirical calculations. Recent time-dependent experiments (Lewis F. D.; Liu, X.; Liu, J.; Hayes, R. T.; Wasielewski, M. R. J. Am. Chem. Soc. 2000, 122, 12037) gave a value of 0.08 eV for this energy gap.
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During the revision of this manuscript, a paper by Petrov et al. (Petrov, E. G.; Schevchenko, Ye. V.; May, V. Chem. Phys. 2003, 288, 269) was published with an identical phenomenological hopping constant as our eq 3. We would like to emphasize that our result was obtained independently and was presented in May 2002 at a meeting of the Electrochemical Society in Philadelphia, PA (U.S.A.), in May 2002 in a talk at Free University Berlin (Germany), and in November 2002 in talks at University of Nagoya, Kyoto University, and Tsukuba University (Japan).
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G,GGG increases, and therefore, the overall, yield decreases for short bridge length.
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