dorsal/arxiv
View SchemaAnharmonic force field and vibrational frequencies of tetrafluoromethane (CF$_4$) and tetrafluorosilane (SiF$_4$)
| Authors | Xiao-Gang Wang, Edwin L. Sibert III, Jan M. L. Martin |
|---|---|
| Categories | |
| ArXiv ID | physics/9909032 |
| URL | https://arxiv.org/abs/physics/9909032 |
| DOI | 10.1063/1.481590 |
| Journal | Journal of Chemical Physics 112, 1353-1366 (2000) |
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.
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"abstract": "Accurate quartic anharmonic force fields for CF$_4$ and SiF$_4$ have been\ncalculated using the CCSD(T) method and basis sets of $spdf$ quality. Based on\nthe {\\it ab initio} force field with a minor empirical adjustment, the\nvibrational energy levels of these two molecules and their isotopomers are\ncalculated by means of high order Canonical Van Vleck Perturbation Theory(CVPT)\nbased on curvilinear coordinates. The calculated energies agree very well with\nthe experimental data. The full quadratic force field of CF$_4$ is further\nrefined to the experimental data. The symmetrization of the Cartesian basis for\nany combination bands of $T_d$ group molecules is discussed using the circular\npromotion operator for the doubly degenerate modes, together with tabulated\nvector coupling coefficients. The extraction of the spectroscopic constants\nfrom our second order transformed Hamiltonian in curvilinear coordinates is\ndiscussed, and compared to a similar procedure in rectilinear coordinates.",
"arxiv_id": "physics/9909032",
"authors": [
"Xiao-Gang Wang",
"Edwin L. Sibert III",
"Jan M. L. Martin"
],
"categories": [
"physics.chem-ph",
"physics.comp-ph"
],
"doi": "10.1063/1.481590",
"journal_ref": "Journal of Chemical Physics 112, 1353-1366 (2000)",
"title": "Anharmonic force field and vibrational frequencies of tetrafluoromethane (CF$_4$) and tetrafluorosilane (SiF$_4$)",
"url": "https://arxiv.org/abs/physics/9909032"
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