Caesium hydride: MS-CASPT2 potential energy curves and A1Σ+→X1Σ+ absorption/emission spectroscopy

Correlated ab initio methods (CASPT2 and CCSD(T)) in conjunction with the ANO-RCC basis sets were used to calculate potential energy curves (PECs) of the ground, valence, and Rydberg electronic states of CsH with the inclusion of the scalar relativistic effects. The spectroscopic constants of bound...

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Bibliographic Details
Published in:The Journal of chemical physics 2017-03, Vol.146 (10), p.104304-104304
Main Authors: Škoviera, Ján, Neogrády, Pavel, Louis, Florent, Pitoňák, Michal, Černušák, Ivan
Format: Article
Language:English
Subjects:
Absorption
Anharmonicity
Banded structure
Cesium
Cesium hydrides
Chemical Physics
Chemical Sciences
Electron states
Emission spectra
Energy levels
Fine structure
Mathematical models
Numerical integration
or physical chemistry
Physics
Potential energy
Relativistic effects
Schrodinger equation
Spectrum analysis
Theoretical and
Wave functions
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Summary:Correlated ab initio methods (CASPT2 and CCSD(T)) in conjunction with the ANO-RCC basis sets were used to calculate potential energy curves (PECs) of the ground, valence, and Rydberg electronic states of CsH with the inclusion of the scalar relativistic effects. The spectroscopic constants of bound states were calculated from the PECs and compared with previous theoretical and/or available experimental data. Absorption and emission spectra arising from the transition between X1Σ+ and A1Σ+ states were modelled using vibrational and rotational energy levels and corresponding nuclear wave functions obtained via the direct numerical integration of one-dimensional rovibrational Schrödinger equation in the CASPT2/ANO-RCC electronic potentials. The anharmonic shape of the A1Σ+ potential and the shape of the pertinent vibrational wave functions have an interesting impact on the final shape of the spectrum and result in the complicated fine structure of individual emission bands.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4978065