Mode-specific quantum rate effects for interfacial electron transfer: computational case studies based upon 4-cyano-N-methylpyridinium reduction
作者： Donald C. Selmarten , Joseph T. Hupp
DOI: 10.1039/FT9969203909
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摘要: Multi-mode quantum rate theory is used to examine the interfacial kinetics of a prototypical organic-radical-generating reaction: reduction 4-cyano-N-methylpyridinium cation. Charge-transfer-enhanced Raman scattering experiments (R. L. Blackbourn, et al., J. Phys. Chem., 1991, 95, 10535) previously showed that 13 vibrational modes are coupled process. From time-dependent analysis spectrum, precise coordinate displacement and reorganizational parameters for each have now been determined. These parameters, when incorporated into theory, yielded an extremely detailed—perhaps unprecedented—description electrochemical reaction kinetics, including complete descriptions of: (a) mode-specific barrier effects, (b) tunnelling (c) non-classical activation effects (d) sum-over states driving force effects.
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