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Consistent scheme for computing standard hydrogen electrode and redox potentials
Author(s) -
Matsui Toru,
Kitagawa Yasutaka,
Okumura Mitsutaka,
Shigeta Yasuteru,
Sakaki Shigeyoshi
Publication year - 2012
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23100
Subject(s) - standard electrode potential , redox , gibbs free energy , aqueous solution , chemistry , standard hydrogen electrode , deprotonation , scheme (mathematics) , molecule , thermodynamics , potential energy , electrode , computational chemistry , electrochemistry , inorganic chemistry , physics , reference electrode , atomic physics , mathematics , organic chemistry , mathematical analysis , ion
The standard hydrogen electrode (SHE) potential in aqueous solution was evaluated with new computational procedure that provides the Gibbs energy of a proton in aqueous solution from the experimental p K a value and the Gibbs energy change by deprotonation reactions of several neutral alcohol molecules. With our computational scheme, the CCSD(T)/aug‐cc‐pVDZ method provides the SHE potential of 4.52 V, which is almost the same as the experimental SHE potential. This scheme also reproduces well the redox potentials of several typical reactions within almost 0.1 V. B3LYP also gives excellent redox potentials of the same reactions with almost the same accuracy with our new computational scheme. © 2012 Wiley Periodicals, Inc.