Ab initio study of the spectroscopy of (CH3)(3)CN and (CH3)(2)CHN.
Using the complete active space self-consistent field (CASSCF) method with 6-311++g(3df,3pd) basis sets, a few electronic states of nitrenes (CH3)3CN and (CH3)2CHN and their positive ions are calculated. All calculated states are valence states, and their characteristics are discussed in detail. In order to investigate the Jahn-Teller effect on (CH3)3CN radical, Cs symmetry was used for (CH3)3CN and (CH3)2CHN in the calculations. The results of our calculations (CASPT2 adiabatic excitation energies and RASSI oscillator strengths) suggest that the calculated transitions of (CH3)3CN at 27,710 cm(-1) and (CH3)2CHN at 28,110 cm(-1) are attributed to 23A'' --> 13A'', while those of (CH3)3CN at 28,916 cm(-1) and (CH3)2CHN at 29,316 cm(-1) are attributed to 13A' --> 13A''. The vertical and adiabatic ionization energies were obtained to compare with the photoelectron spectroscopic data. These results are in agreement with previous experimental data. Also, we present a comprehensive review on the CAS calculation results for (CH3)nCH(3-n)N (n = 0-3) presented in our previous and present papers.
Hou
Chun-Yuan
CY
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry Jilin University, Changchun, China.
Zheng
Qing-Chuan
QC
Zhao
Zeng-Xia
ZX
Zhang
Hong-Xing
HX