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Low-lying electronic states of HNCS and its ions: a CASSCF/CASPT2 study

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Abstract

Complete active space self-consistent-field (CASSCF) and multiconfigurational second-order perturbation theory (CASPT2) calculations in conjunction with the ANO-L basis set were performed to investigate systematically the low-lying electronic states of HNCS and its ions in C s symmetry. Our highly accurate calculation indicated that theoretically determined geometric parameters and harmonic vibrational frequencies for the ground-state X 1A′ are in good agreement with observed experimental data. The geometry of triplet HNCS is clearly favored C 1 symmetry, and the relative energy is predicted to be 3.000 eV (69.2 kcal/mol). The vertical transition energies for the selected excited states of HNCS were calculated at CASSCF/CASPT2/ANO-L level of theory based on CASSCF optimized geometry. Except for a few linear states of X 2Π (12A′, 12A″), 14Σ− (14A″), and 12Σ+ (32A′) states of HNCS+, our results confirmed that the majority of excited states are twisted trans-bend structures. The existence of bound excited anion states has been found for the first time in HNCS−. A more elaborate examination of ionization potential of HNCS (AIP, VIP) than previous reports has been presented.

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Acknowledgments

This work was supported by the Natural Science Foundation of China (Grant No. 20973076).

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Authors and Affiliations

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, 130023, Changchun, People’s Republic of China

    Tao Liu, Zeng-Xia Zhao, Ming-Xing Song, Hong-Xing Zhang & Chia-Chung Sun

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  1. Tao Liu
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  2. Zeng-Xia Zhao
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  3. Ming-Xing Song
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Correspondence to Hong-Xing Zhang.

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Liu, T., Zhao, ZX., Song, MX. et al. Low-lying electronic states of HNCS and its ions: a CASSCF/CASPT2 study. Theor Chem Acc 128, 215–222 (2011). https://doi.org/10.1007/s00214-010-0833-4

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