Chem. J. Chinese Universities ›› 2009, Vol. 30 ›› Issue (9): 1839.

• Articles • Previous Articles     Next Articles

Theoretical Investigation on Halocyanocarbene XCCN(X=F, Cl, Br)

ZHAO Zeng-Xia, HOU Chun-Yuan, ZHANG Hong-Xing*, SUN Chia-Chung   

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China
  • Received:2008-09-02 Online:2009-09-10 Published:2009-09-10
  • Contact: ZHANG Hong-Xing. E-mail: zhanghx@mail.jlu.edu.cn
  • Supported by:

    国家自然科学基金(批准号: 20573042, 20173021和20333050)资助.

Abstract:

Complete the calculations by means of the active space self-consistent field method(CASSCF) with ANO-S basis sets was performed on the ground and low-lying electronic excited states of halocyanocarbene XCCN and their anions, with X=F, Cl and Br. Our results show that XCCN have triplet X 3A″ neutral ground states and the singlet-triplet energy gaps ΔES-T(kJ/mol) follow this order: 7.4(FCCN)<13.4(ClCCN)<16.6(BrCCN). The calculated most intensive vertical excitation energies of X3A″→23A″ transitions for FCCN, ClCCN, and BrCCN at 408.3, 385.4 and 345.2 kJ/mol, respectively, are mainly attributed to the π(a′)→nxy transitions. The adiabatic electron affinities for XCCN are found to be 235.7, 233.0 and 237.2 kJ/mol, respectively. Compared with the results of HCCN, the electron affinities are enhanced.

Key words: Halocyanocarbene; Complete-active-space self-consistent field; Complete-active-space second-order perturbation; Singlet state; Triplet state

TrendMD: