Abstract
An infrared double-resonance experiment has been carried out on fluoroform-d. The ν2←0 and ν5←0 fundamentals have been reanalyzed at a resolution of 0.001 cm−1. From excited-state absorptions in the ν2+ν5←ν5 and 2ν5←ν5 bands, we obtain values for the anharmonicity constants x25=−1.0 cm−1, x55=−0.23 cm−1, and g55=0.13 cm−1. Both of the xk5 values are in good agreement with Dennison’s rule estimates of Kirk and Wilt. Collision-induced double-resonance signals indicate propensity rules for rotational state changes ΔJ=±1, ΔK=±3n, where n may take integer values as large as 6 or 8. The rotational relaxation rates are three to five times hard-sphere gas kinetic for polar collision partners (CDF3 itself or CH2F2), but only one-fifth gas kinetic for helium collisions. These results are used to assess proposed models for multiple infrared photon dissociation in CDF3 and for submillimeter-wave optically pumped laser action in this gas.
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