Long-range electron and charge transfers in peptide bridging phthalimide and methyl aminoacetate radical systems: Super-exchange and hopping mechanisms

Super-exchange and hopping mechanisms and distance dependence of long-range electron transfer (ET) and charge transfer (CT) in pa-(gly)n=0–6-aa (pa = C6H4(CO)2N-(CH2CO), gly = glycine, aa = HNCH2COOCH3) ionic molecules have been explored by computational studies of ET matrix element VPS, ET rate constant kET and reorganization energies using two-state variational method (TSVM) and classical and semi-classical rate models. For comparison electron correlation effects are examined in the calculations. Calculated distance dependences of kET are in good agreement with the experimental predictions. These results are then used to elucidate ET and CT reaction mechanisms.