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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