TY - JOUR
T1 - Free energy profiles of electron transfer at water-electrode interface studied by the reference interaction site model theory
AU - Akiyama, Ryo
AU - Kinoshita, Masahiro
AU - Hirata, Fumio
N1 - Funding Information:
The authors are grateful to Dr. Hirofumi Sato and Mr. Takashi Imai for their help in computations and discussions. RA is supported by Research Fellowships of the Japan Society for the Promotion of Science for Young Scientists. This work is supported by Grant-in-Aid for Scientific Research on Priority Area of `Electrochemistry of Ordered Interfaces' (No. 09237265) from Ministry of Education, Sports and Culture, Japan.
PY - 1999/5/21
Y1 - 1999/5/21
N2 - Free energy profiles governing electron transfer from a reactant to an electrode surface in water are investigated, based on the reference interaction site model (RISM) theory. Three models of a redox pair for charge separation reactions are examined: a pair of atomic solutes, and systems consisting of an atom and a surface with a localized or a delocalized electron. The profile becomes highly asymmetrical, when an electron in the electrode is delocalized. The behaviors are essentially due to the asymmetrical response of water polarization to positive and negative charges of solute. The results are related to models of ion-hydration.
AB - Free energy profiles governing electron transfer from a reactant to an electrode surface in water are investigated, based on the reference interaction site model (RISM) theory. Three models of a redox pair for charge separation reactions are examined: a pair of atomic solutes, and systems consisting of an atom and a surface with a localized or a delocalized electron. The profile becomes highly asymmetrical, when an electron in the electrode is delocalized. The behaviors are essentially due to the asymmetrical response of water polarization to positive and negative charges of solute. The results are related to models of ion-hydration.
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U2 - 10.1016/S0009-2614(99)00372-3
DO - 10.1016/S0009-2614(99)00372-3
M3 - Article
AN - SCOPUS:0001618413
SN - 0009-2614
VL - 305
SP - 251
EP - 257
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 3-4
ER -