TY - JOUR
T1 - Removal of the double adiabatic approximation for proton-coupled electron transfer reactions in solution
AU - Soudackov, Alexander V.
AU - Hammes-Schiffer, Sharon
N1 - Funding Information:
We would like to thank Dr. Jian-Yun Fang and Dr. Simon Webb for helpful discussions. We are grateful for financial support from the NSF CAREER program Grant CHE-9623813 and the Clare Boothe Luce Foundation. S.H.S. is the recipient of an Alfred P. Sloan Foundation Research Fellowship.
PY - 1999/1/16
Y1 - 1999/1/16
N2 - A dynamical theory that removes the double adiabatic approximation for proton-coupled electron transfer reactions in solution is presented. In this formulation mixed electronic/proton vibrational adiabatic states are expressed as linear combinations of double adiabatic states that each correspond to the product of an electronic and a proton vibrational state. This methodology includes all nonadiabatic coupling terms in a computationally practical way. The electron-proton nonadiabatic coupling is incorporated into the adiabatic states, while the electron-solvent and proton-solvent nonadiabatic couplings are incorporated through nonadiabatic transitions among these states. Two model proton-coupled electron transfer reactions are investigated.
AB - A dynamical theory that removes the double adiabatic approximation for proton-coupled electron transfer reactions in solution is presented. In this formulation mixed electronic/proton vibrational adiabatic states are expressed as linear combinations of double adiabatic states that each correspond to the product of an electronic and a proton vibrational state. This methodology includes all nonadiabatic coupling terms in a computationally practical way. The electron-proton nonadiabatic coupling is incorporated into the adiabatic states, while the electron-solvent and proton-solvent nonadiabatic couplings are incorporated through nonadiabatic transitions among these states. Two model proton-coupled electron transfer reactions are investigated.
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U2 - 10.1016/S0009-2614(98)01347-5
DO - 10.1016/S0009-2614(98)01347-5
M3 - Article
AN - SCOPUS:0008119361
SN - 0009-2614
VL - 299
SP - 503
EP - 510
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 5
ER -