The hydroxyl groups internal rotations in a methanediol molecule
| Autor: | V. V. Sapeshko, A.Ye. Malevich, G. A. Pitsevich |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
Physics
Hamiltonian matrix 010304 chemical physics Dihedral angle 010402 general chemistry 01 natural sciences Potential energy Molecular physics Atomic and Molecular Physics and Optics 0104 chemical sciences Dipole chemistry.chemical_compound chemistry Methanediol ЕСТЕСТВЕННЫЕ И ТОЧНЫЕ НАУКИ::Физика [ЭБ БГУ] 0103 physical sciences Potential energy surface Molecular symmetry Physical and Theoretical Chemistry Spectroscopy Basis set |
| Zdroj: | Journal of Molecular Spectroscopy. 360:31-38 |
| ISSN: | 0022-2852 |
| DOI: | 10.1016/j.jms.2019.04.013 |
| Popis: | Internal rotation of two of hydroxyl groups in a methanediol molecule is analyzed by constructing the 2D surfaces of the potential energy, kinematic coefficients and dipole moment. The molecular characteristics in the nodes of 2D grids with different densities for distinct pairs of dihedral angles of O H groups were calculated at the MP2/cc-pVQZ level of theory with optimization of the geometry for all other structural parameters. For optimized at the MP2/cc-pVQZ level of theory geometries, the potential energy was additionally calculated at the MP2/cc-pVTZ level of theory in the same grid nodes and then the extrapolation of energies in every node to the complete basis set limit was performed. The kinematic parameters were calculated using the formalism of the Wilson vectors. The Hamiltonian matrix was compiled using the DVR method. As a result of its diagonalization, the wave functions and energies of stationary torsional states were determined. The calculated torsional wave functions were classified by irreducible representations of the C2V(M) molecular symmetry group. The frequencies and intensities of the torsional spectrum of a methanediol molecule were calculated at different temperatures for the trans- and cis-conformers. The tunneling frequencies for both conformers were calculated too. |
| Databáze: | OpenAIRE |
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