Ab initio study of spectroscopic properties at anharmonic force fields of LiNH2
- 8 January 2021
- journal article
- research article
- Published by Springer Science and Business Media LLC in Journal of Molecular Modeling
- Vol. 27 (2), 1-13
- https://doi.org/10.1007/s00894-020-04641-9
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)
Keywords
This publication has 37 references indexed in Scilit:
- Lithium Amide (LiNH2) Under PressureThe Journal of Physical Chemistry A, 2012
- First Principles Study of the LiNH2/Li2NH TransformationThe Journal of Physical Chemistry C, 2010
- Density functional theory study on (LiNH2)n (n = 1–5) clustersJournal of Molecular Modeling, 2010
- Ab initio study of spectroscopic constants and anharmonic force field of Ge74Cl2The Journal of Chemical Physics, 2007
- Decomposition Kinetics of Lithium Amide and Its Implications for Hydrogen StorageMRS Proceedings, 2004
- Interaction of hydrogen with metal nitrides and imidesNature, 2002
- ChemInform Abstract: Solution Structures of Lithium Dialkylamides and Related N-Lithiated Species: Results from 6Li-15N Double Labeling ExperimentsChemInform, 1993
- Local-mode to normal-mode hamiltonian transformation forX-H stretchingsMolecular Physics, 1988
- N-Monosubstituted 2-Aminopyridines, 2-Aminopyrimidines and 2-AminolepidinesJournal of the American Chemical Society, 1951
- Note on an Approximation Treatment for Many-Electron SystemsPhysical Review B, 1934