High-resolution infrared study of the 2ν3 (A1, E) and ν1 + ν3 (E) bands of 14NF3

The 2ν3 overtone (A1, E) and the ν1 + ν3 (E) combination bands of the oblate symmetric top 14NF3 were studied by FTIR spectroscopy with a resolution of 2.5 × 10−3 cm−1. Nearly 500 lines up to Kmax/Jmax = 30/43 were observed for the weak A1 component reaching the v3 = 20 substate (1803.1302 cm−1), the majority of which corresponded to reinforced K = 3p-type transitions. For the strong E component reaching the v3 = 2±2 substate (1810.4239 cm−1), about 3550 transitions were assigned up to Kmax/Jmax = 65/69, favoring a clear observation of the ℓ(4, −2) and ℓ(4, 4) splittings within the kℓ = −2 and +4 sublevels, respectively. The two v3 = 2 substates are linked by the ℓ(2, 2)- and ℓ(2, −1)-type interactions, providing severe crossings, respectively, at K′ = 6 and near K′ = 24 on the v3 = 2+2 side. A model working in the D-reduction and including all these ℓ-type interactions could reproduce together 3695 nonzero weighted experimental data (NZW) through 33 free parameters with a standard deviation of σ = 0.357 × 10−3  cm−1. As for the ν1 + ν3 (E) combination band, about 3690 lines were assigned up to Kmax/Jmax = 45/55. Its v1 = v3 = 1 upper state (1931.577 5 cm−1) was treated using the same model recently applied to the v3 = 1 (E, 907.5413 cm−1) state. It yielded 21 free parameters through 3282 NZW experimental data, adjusted with σ = 0.344 × 10−3  cm−1 in the D-reduction. For the two excited states, the small and unobserved ℓ(0, 6) interaction was tested as useless. To confirm the adequacy of the vibrationally isolated models used, some other reductions of the Hamiltonian were tried. For the v3 = 2 state, the D-, L-, and LD-reductions led to similar σ's, while the Q one was not successful. For the v1 = v3 = 1 state, the D- and Q-reductions gave comparable σ's, while the QD-reduction was not as good. The corresponding unitary equivalence relations are generally more nicely fulfilled for the v3 = 2 state than for the v1 = v3 = 1 state. The three derivable anharmonicity constants in cm−1 are x33 = −4.1528, g33 = +1.8235 and x13 = −7.9652.