Electrochemical reduction of the O2 molecule to the O2- radical ion -: A theoretical approach

被引：22

作者：

Ignaczak, A ^{[1
]}

Schmickler, W ^{[1
]}

Bartenschlager, S ^{[1
]}

机构：

[1] Univ Ulm, Dept Theoret Chem, D-89069 Ulm, Germany

来源：

JOURNAL OF ELECTROANALYTICAL CHEMISTRY | 2006年 / 586卷 / 02期

关键词：

oxygen reduction; superoxide ion; quantum calculations; eigen functions; non-adiabatic electron transfer theory; reaction rate;

D O I：

10.1016/j.jelechem.2005.09.020

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

Quantum effects in the kinetics of the reaction O-2 + e -> O-2(-) have been evaluated theoretically. The spectral properties and the potential energy curves of the oxygen molecule and the superoxide ion were obtained from quantum DFT calculations at the G96PW91/6-311+G* level. From these curves, the vibrational eigenfunctions and eigenvalues of the reactant and the product were calculated. The corresponding non-adiabatic reduction rate was obtained from first-order perturbation theory. The partial contributions coming from the ground and excited states of both species are analyzed in detail. It is shown that the contribution of the O-2(-) excited states to the rate is negligibly small for low overpotentials. Their participation rises when higher overpotentials are applied. (c) 2005 Elsevier B.V. All rights reserved.

引用

页码：297 / 307

页数：11

共 42 条

[1] Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters:: The mPW and mPW1PW models [J].