Geometries and energies of nitrobenzene studied by CAS-SCF calculations

被引：74

作者：

Takezaki, M ^{[1
]}

Hirota, N ^{[1
]}

Terazima, M ^{[1
]}

Sato, H ^{[1
]}

Nakajima, T ^{[1
]}

Kato, S ^{[1
]}

机构：

[1] KYOTO UNIV,GRAD SCH SCI,DEPT CHEM,KYOTO 606,JAPAN

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 1997年 / 101卷 / 28期

关键词：

D O I：

10.1021/jp970937v

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Optimized geometries and energies in the ground (S-0) and excited states of nitrobenzene were calculated using the CAS-SCF method. The optimized geometries in the S-1, S-2, T-1, T-2, and T-3 states are very different from that in the S-0 state. Most significantly, the nitro group is largely bent out of the phenyl plane in the excited states. The potential curves along the nitro rotation coordinate around the C-N bond and the out-of-plane bending mode of the nitro group in the S-0, S-1, T-1, and T-2 states were calculated in relation to the excited states dynamics. It is found that the potential curves along the bending mode in the excited states are very flat compared with that in the S-0 state. The mechanisms for the fast relaxation from the S-1 and T-1 states are discussed based on the ab initio results.

引用

页码：5190 / 5195

页数：6

共 36 条

[21] SOLVENT EFFECTS ON ELECTRONIC ABSORPTION-SPECTRA OF NITROCHLOROBENZENES, NITROPHENOLS AND NITROANILINES .1. STUDIES IN NONPOLAR-SOLVENTS [J].