High-resolution infrared and millimeterwave spectra of the v3=1 vibrational state of NF3 at 907 cm

The ν₃^±1 perpendicular band of ¹⁴NF₃ ( cm⁻¹) has been studied with a resolution of 2.5 × 10⁻³ cm⁻¹, and 3682 infrared (IR) transitions (J_max=55, K_max=45) have been assigned. These transitions were complemented by 183 millimeterwave (MMW) rotational lines (J_max=25, K_max=19) in the 150–550 GHz region (precision 50–100 kHz). The kl=+1 level reveals a strong A₁/A₂ splitting due to the l(2,2) rotational interaction (q=−4.05 × 10⁻³ cm⁻¹) while the kl=−2 and +4 levels exhibit small A₁/A₂ splittings due to l(2,−4) and l(0,6) rotational interactions. All these splittings were observed by both experimental methods. Assuming the v₃=1 vibrational state as isolated, a Hamiltonian model of interactions in the D reduction, with l(2,−1) rotational interaction (r=−1.96 × 10⁻⁴ cm⁻¹) added, accounted for the observations. A set of 26 molecular constants reproduced the IR observations with σ_IR=0.175 × 10⁻³ cm⁻¹ and the MMW data with σ_MMW=134 kHz. The Q reduction was also performed and found of comparable quality while the QD reduction behaved poorly. This may be explained by a predicted Coriolis interaction between v₃=1 and v₁=1 (A₁, 1032.001 cm⁻¹) which induces a slow convergence of the Hamiltonian in the QD reduction but has no major influence on the other reductions. The experimental equilibrium structure could be calculated as: r_e(N–F)=1.3676 Å and (FNF)=101.84°.