物理化学学报2006，Vol.22Issue(9)：1079-1084,6.
反式和顺式HOOOH的电子光谱的理论研究
Theoretical Study on the Electronic Spectra of cis-HOOOH and trans-HOOOH
摘要
Abstract
Equilibrium geometries of cis-HOOOH and trans-HOOOH have been investigated using the density functional theory (DFT), complete active space self-consistent-field (CASSCF), and coupled cluster with single and double replacement (CCSD) approaches. The harmonic vibrational frequencies on the optimized geometries were calculated using the DFT theory. The potential energy curve of the isomerization between the trans-HOOOH and cisHOOOH was obtained by DFT calculations. Time-dependent density functional theory (TD-DFT) and complete active space perturbation theory of second order (CASPT2) calculations have been performed to obtain the vertical excitation energies of selected low-lying singlet and triplet excited states. Computed results show that: (1) trans-isomer is more stable than cis-isomer; (2) there are two pathways of the conversion between the trans-HOOOH and cis-HOOOH; (3)the vertical excitation energies of the lowest singlet and triplet excited states in trans-HOOOH are lower than those in cis-isomer; (4) in the singlet excited states, 21A state in trans-HOOOH and 21A" state in cis-HOOOH have the longest lifetimes of 2.07×10-5 s and 1.44×10-5 s with the excitation energies of 165.52 and 167.43 nm, respectively.关键词
DFT/CASPT2/HOOOH/过渡态/电子光谱Key words
DFT, CASPT2, HOOOH, Transition state, Electronic spectra分类
化学化工引用本文复制引用
王连宾,吴文鹏,张敬来,曹泽星..反式和顺式HOOOH的电子光谱的理论研究[J].物理化学学报,2006,22(9):1079-1084,6.基金项目
国家自然科学基金(20473062,20233020,20021002,20173042)、厦门大学固体表面物理化学国家重点实验室开放课题基金(200306)、河南省自然科学基金(0311011200,200510475012)资助项目 （20473062,20233020,20021002,20173042）
