Ab initio study of the spectroscopy of (CH3)(3)CN and (CH3)(2)CHN

Chun-Yuan Hou; Qing-Chuan Zheng; Zeng-Xia Zhao; Hong-Xing Zhang

doi:10.1021/jp072017a

Ab initio study of the spectroscopy of (CH3)(3)CN and (CH3)(2)CHN

J Phys Chem A. 2007 Nov 29;111(47):12037-41. doi: 10.1021/jp072017a. Epub 2007 Nov 7.

Authors

Chun-Yuan Hou¹, Qing-Chuan Zheng, Zeng-Xia Zhao, Hong-Xing Zhang

Affiliation

¹ State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry Jilin University, Changchun, China.

PMID: 17985848
DOI: 10.1021/jp072017a

Abstract

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.