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Ab initio study of spectroscopic properties at anharmonic force fields of LiNH2

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Abstract

This work presents a systematic investigation of the spectroscopic properties at anharmonic force fields of ground electronic state (\( {\tilde{X}}^1{A}_1 \)) of LiNH2, which are calculated using second-order Møller-Plesset perturbation theory (MP2) and density functional theory (DFT) with hybrid GGA and meta-hybrid GGA (M06-2X) exchange-correlation functional. Two high angular momentum basis sets of 6-311+g (2d, p) and 6-311++g (3df, 2pd) are used. The equilibrium geometries, ground-state rotational constants, harmonic frequencies, and quartic and sextic centrifugal distortion constants of LiNH2 are calculated and compared with corresponding experimental or theoretical data. The predicted accuracy of the calculated constants has been confirmed by analyzing the deviations with respect to experiment. In addition, the anharmonic constants, vibration-rotation interaction constants, force constants, and Coriolis coupling constants of LiNH2 are firstly obtained. The infrared spectrum is predicted and together with the first prediction on the higher-order anharmonic constants contributes to a better understanding of the vibrational and rotational characteristics of LiNH2, thus revealing its internal structure.

The IR spectra and the magnified IR spectra at 3500 cm−1 in harmonic approximations of LiNH2 using B3P86, M06-2X and MP2 methods combining with 6-311++g(3df,2pd)

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Data availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Funding

This work was supported by the National Natural Science Foundation of China (Grant No.11474142) as well as the Taishan Scholars Project of Shandong Province (ts2015 11055). All calculations were carried out at the Langchao Supercomputer Center (LCSCC) of Ludong University.

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Authors and Affiliations

  1. School of Physics and Optoelectronics Engineering, Ludong University, Yantai, 264025, China

    Shanshan Ma, Meishan Wang, Yanli Liu, Chuanlu Yang, Lihan Chi & Qiushuang Xu

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  1. Shanshan Ma
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Contributions

Shanshan Ma: Writing – original draft preparation, Methodology, Data curation.

Meishan Wang: Software, Supervision, and Writing – reviewing and editing.

Yanli Liu: Writing – reviewing and editing.

Chuanlu Yang: Project administration.

Lihan Chi: Formal analysis.

Qiushuang Xu: Formal analysis.

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Correspondence to Meishan Wang.

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Ma, S., Wang, M., Liu, Y. et al. Ab initio study of spectroscopic properties at anharmonic force fields of LiNH2. J Mol Model 27, 33 (2021). https://doi.org/10.1007/s00894-020-04641-9

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