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Updated: Aug 9, 2026

Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
Published on: July 19, 2019
Isotope effect on electron transfer in reaction centers from Rhodopseudomonas sphaeroides
1Department of Physics, University of California, San Diego, La Jolla, CA 92093.
Abstract:
Previous ENDOR studies on reaction centers from Rhodopseudomonas sphaeroides have shown the presence of two hydrogen-bonded protons associated with the primary, ubiquinone, acceptor Q(A). These protons exchange with deuterons from solvent (2)H(2)O. The effect of this deuterium substitution on the charge-recombination kinetics (BChl)(2) (+)Q(A) (-) --> (BChl)(2)Q(A) has been studied with a sensitive kinetic difference technique. The electron-transfer rate was found to increase with deuterium exchange up to a maximum Deltak/k of 5.7 +/- 0.3%. The change in rate was found to have an exchange time of 2 hr, which matched the disappearance of the ENDOR lines due to the exchangeable protons. These results indicate that these protons play a role in the vibronic coupling associated with electron transfer. A simple model for the isotope effect on electron transfer predicts a maximum rate increase of 20%, which is consistent with the experimental results.
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