Anharmonic force field and vibrational frequencies of tetrafluoromethane (CF${}_4$) and tetrafluorosilane (SiF${}_4$)

Abstract

Accurate quartic anharmonic force fields for CF${}_4$ and SiF${}_4$ have been calculated using the CCSD(T) method and basis sets of $spdf$ quality. Based on the {\it ab initio} force field with a minor empirical adjustment, the vibrational energy levels of these two molecules and their isotopomers are calculated by means of high order Canonical Van Vleck Perturbation Theory(CVPT) based on curvilinear coordinates. The calculated energies agree very well with the experimental data. The full quadratic force field of CF${}_4$ is further refined to the experimental data. The symmetrization of the Cartesian basis for any combination bands of $T_d$ group molecules is discussed using the circular promotion operator for the doubly degenerate modes, together with tabulated vector coupling coefficients. The extraction of the spectroscopic constants from our second order transformed Hamiltonian in curvilinear coordinates is discussed, and compared to a similar procedure in rectilinear coordinates.

(submitted to J. Chem. Phys.)

References in corpus (5)

• Boson-realization model for the vibrational spectra of tetrahedral molecules
• A fully ab initio quartic force field of spectroscopic quality for SO_3
• A definitive heat of vaporization of silicon through benchmark ab initio calculations on SiF_4
• Overtone spectra and intensities of tetrahedral molecules in boson-realization models
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