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Ab initio study of the structure, force field, and vibrational spectrum of the LiClO3 molecule

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Abstract

The geometrical structure and the vibrational spectrum of the LiClO3 molecule are studied by the Hartree-Fock-Roothaan (HF) and configurational interaction (CI) methods taking into account single and double excitations and Davidson's correction for quadruple excitations. Double-zeta basis sets of Huzinaga-Dunning and McLean-Chandler complemented with polarization and diffuse functions are used. Potential surface sections corresponding to migration of the Li+ cation around the ClO −3 fragment are investigated. It was found that the LiClO3 molecule has a single stable configuration of Cs symmetry with the bidentate coordination of the Li+ cation by the ClO −3 anion. The cyclic fragment

is nonplanar (the dihedral angle θ(LiO2Cl)=173°). The tridentate configuration of C3v symmetry lies higher than the equilibrium configuration by 24.5 (HF) or 18.3 (CI) kJ/mole and is not an isomer. The ab initio force field of the molecule was refined by the scaling method. Some assignments of the IR bands of the matrix-isolated molecular forms existing in vapor over lithium chlorate are corrected. The vibration frequencies (cm−1) and IR intensities (km/mole; in parentheses) are calculated with the refined force field: A′ type 1099(236), 856(81), 630(73), 557(119), 481(87), 156(66); A″ type 887(229), 459(35), 367(23).

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Authors
  1. V. G. Solomonik
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  2. T. P. Pogrebnaya
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  3. V. V. Sliznev
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Additional information

Ivanovo State Chemical Technological Academy. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 3, pp. 440–449, May–June, 1996.

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Solomonik, V.G., Pogrebnaya, T.P. & Sliznev, V.V. Ab initio study of the structure, force field, and vibrational spectrum of the LiClO3 molecule. J Struct Chem 37, 384–391 (1996). https://doi.org/10.1007/BF02578590

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  • DOI: https://doi.org/10.1007/BF02578590

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