Abstract
The equilibrium geometrical parameters, force constants, vibration frequencies, IR intensities, and isomerization and dissociation energies of MAF4 molecules are calculated by Hartree-Fock and second-order Möller — Plessett perturbation theory methods in the Li (9s3pld/4s3pld), Na, Al (12s8pld/6s4pld), K (14s11p3d/9s8p3d), F (9s5pld/4s2pld), and Ga (13s10p5d/6s5p2d) bases of grouped Gaussian functions. The calculations show that the structures corresponding to the bi-(b) and tridentate (t) coordinations of the M+ cation by the AF -4 anion are isomers. The b configuration is energetically most favorable for LiAF4 molecules. The b and t structures of NaAF4 have close energies, and the t configuration is basic for KAF4 molecules. Simple empirical relations between the molecular constants in the series LiAF4→NaAF4→KAF4 are found and the molecular parameters of RbAF4 and CsAF4 are estimated. A combined analysis of the ab initio and experimental data available in the literature for MAF4 molecules is carried out. A number of bands observed in the IR spectrum of the matrix-isolated MAlF4 molecules are assigned to their tridentate isomer.
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Solomonik, V.G., Sliznev, V.V. Ab initio study of the molecular structure, isomerism, and vibrational spectra of MAF4. (M = Li, Na, K; A = Al, Ga). J Struct Chem 40, 368–379 (1999). https://doi.org/10.1007/BF02700631
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DOI: https://doi.org/10.1007/BF02700631