AB INITIO STUDY OF SCANDIUM FLUORIDE MOLECULES: ScF, ScF2, AND ScF3
V. G. Solomonik, A. A. Mukhanov
Keywords: scandium fluorides, molecular structure and spectra, atomization enthalpy, quantum chemistry, coupled-cluster method, extrapolation to the limit of the complete basis set
Pages: 34-40
Abstract
Equilibrium geometric parameters, normal mode frequencies and intensities in IR spectra, atomization enthalpy, and relative energies of low-lying electronic states of scandium fluoride molecules (ScF, ScF2, and ScF3) are calculated by the coupled-cluster method (CCSD(T)) in triple-, quadruple, and quintuple-zeta basis sets with the subsequent extrapolation of the calculation results to the complete basis set limit. The ScF molecule is also studied by the CCSDT technique. The error in the approximate calculation of triple excitations in the CCSD(T) method does not exceed 0.002 Å for the equilibrium internuclear distance Re, 4 cm-1 for the vibrational frequency, and 0.2 kcal/mol for the dissociation energy of the molecule. In the ground electronic state 2A1(C2v) of ScF2 molecules, Re(Sc-F) = 1.827 Å and αe(F-Sc-F) = 124.2°; the energy barrier to bending (linearization) h = Emin(D∞h) - Emin(C2v) = 1652 cm-1. The relative energies of 2Δg and 2Πg electronic states are 3522 cm-1 and 14633 cm-1 respectively. The bond distance in the ScF3 molecule (, D3h) is refined: Re(Sc-F) = 1.842 Å. The atomization enthalpies Δat of ScFk molecules are 139.9 kcal/mol, 289.0 kcal/mol, and 444.8 kcal/mol for k = 1, 2, 3 respectively.
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