Ketenimine molecule with axes labeled. Geometry optimized via B3LYP/cc-pVTZ calculations. Note: in the I r representation z = a, x = b, and y = c.
(a) Experimental, survey spectrum of ν 7 (region 1) and (b) corresponding simulation. The expanded experimental (c) and simulated (d) sections illustrate the agreement between the two. (a) Intense transitions attributed to the ν 2 mode of HCN centered about 712 cm−1 which do not appear in the simulation. (c) Weak hot-band structure which does not appear in the simulation. Further additional lines are due to residual water.
(a) A section of the recorded far-IR spectrum containing the weak K a = 5–6 Q-branch transitions and (b) simulation based on parameters presented in Table I. The simulation also contains an accurate prediction of the 205,15 ← 194,15 R-branch rotational transition, which is not explicitly fitted, centered about 70.204 cm−1 whilst extra transitions in the experimental spectrum attributed to impurities (probably water, ammonia, or methyl cyanide), which do not appear in the simulation.
Calculated energies of the J = 10 level for K a up to 10 for the lowest energy modes of ketenimine. ν 7 and 2ν 12 energies calculated from parameters in Table II. G.S., ν 12, and ν 8 energies calculated from the parameters in Table I. Some symmetry allowed Coriolis interactions between states are indicated (note: observed Cor-a interactions between ν 12 and ν 8 continue to high K a ). Solid and dashed lines represent observed and predicted levels and interactions, respectively.
Band parameters fitted to Watson's S-reduced I r Hamiltonian for the G.S., ν 8, and ν 12 system of coupled modes of ketenimine. Presented in the frequency units for consistency with previous work.
Band parameters fitted to Watson's S-reduced I r Hamiltonian for the system of coupled modes of ketenimine. Presented in frequency units for consistency with the previous work.
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