Anharmonic force fields and spectroscopic properties of BF3 and CF3+ using the coupled cluster method

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Abstract
Anharmonic force fields and ro-vibrational spectroscopic properties of BF3 and CF3+ have been investigated, using the coupled cluster method with single and double substitutions augmented by a perturbative estimate of triple excitations [CCSD(T)] with a basis set of 120 contracted Gaussian-type orbitals (cGTOs). A complete set of ro-vibrational spectroscopic constants for each species has been calculated using second-order perturbation theory. For BF3 the CCSD(T) equilibrium bond distance is larger than the experimental value by 0.0058 Å, and the fundamental frequencies are within 5 cm−1 of experiment, except for ν3, which shows a deviation of 16 cm−1. The CCSD(T) method yields vibration-rotation interaction constants αe in excellent agreement with available experimental values (within 3 MHz). The CCSD(T) bond distance of CF3+ is 1.2305 Å with a basis set of 220 cGTOs, which is corrected to 1.2272 Å by applying a correction derived from the identical level of calculation on BF3. The fundamental frequencies ν1, ν2, ν3, and ν4 for CF3+ are predicted to be 1044 cm−1, 813 cm−1, 1683 cm−1, and 593 cm−1, respectively.

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