Chem. J. Chinese Universities ›› 2010, Vol. 31 ›› Issue (1): 125.

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ab initio Study on the Spectroscopy of H2CCC

SHU Xin, ZHAO Zeng-Xia, 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:2009-02-24 Online:2010-01-10 Published:2010-01-10
  • 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 active space self-consistent field(CASSCF) calculations with ANO-S basis sets were performed for a few electronic states of propadienylidene, H2CCC, and its cation and anion in C2v symmetry. For all the calculated states, the accuracy of the total energies was improved by including dynamic electron correlation via the multiconfiguration second-order perturbation theory(CASPT2) method. The results suggest that the calculated transitions of X1A1 → 1A2, X1A1 → 1B1 and X1A1 → 21A1 at 159.0, 216.5 and 476.4 kJ/mol are attributed to π(b2)→π*(b1), n(a1)→π*(b1) and π(b1)→π*(b1) transition, respectively. The electron affinities were obtained in comparison with the photoelectron spectrum(PES) data. These above results are in agreement with the previous experimental data.

Key words: Propadienylidene; Completeactivespace selfconsistent field; Completeactive-space secondorder perturbation; Photoelectron spectroscopy

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