文献类型：期刊文献

英文题名：Connection of DFT Molecular Orbital Eigenvalues with the Observable Oxidation Potentials/Oxidation Energies

作者：Chen, Jiang-Hua[1];He, Li-Ming[1];Wang, Richard L.[1]

机构：[1]E China Univ Sci & Technol, Dept Phys, Shanghai 200237, Peoples R China

年份：2013

卷号：117

期号：24

起止页码：5132

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY A

收录：;EI(收录号：20132716460959);WOS:【SCI-EXPANDED(收录号:WOS:000320911000015)】；

语种：英文

外文关键词：Eigenvalues and eigenfunctions - Continuum mechanics - Molecular orbitals

摘要：It is demonstrated that the negative highest occupied molecular orbital eigenvalues of a molecule S in the gas phase, -HOMO(S,g), and in solution, -HOMO (S,s), and the negative lowest unoccupied molecular orbital eigenvalue of its cation S+ in solution, -LUMO(S+,s), are good approximations to the oxidation energy, the energy for removing an electron out of a molecule in solution. This observation is based on the DFT calculations using the B3LYP exchange correlation functional with a basis set of 6-311+G(d,p) and the polarizable continuum model (PCM) for computing solvation energies for a set of 22 middle-size molecules/radicals.