High-Resolution Infrared Spectrum of PH2Br: Rotational Analysis of the ν3 and ν4 Bands

The infrared spectrum of short-lived PH₂Br has been observed by studying the reaction of P₂H₄ with gaseous HBr. The a-type fundamental bands ν₃ at 812 cm⁻¹ and ν₄ at 399 cm⁻¹ have been recorded with a resolution of ca. 5×10⁻³ cm⁻¹, and their rotational fine structure has been observed. While the ν₄ band and its hot band 2ν₄−ν₄ associated with the P-Br stretching reveal compact ^qP and ^qRJ-clusters, the HPBr bending fundamental ν₃ shows a widely dispersed structure. A c-type Coriolis interaction of ν₃ (K_a) with the unobserved ν₆ state (K_a+1) at 795 cm⁻¹, with resonance between K_a=1 and 2, was detected and analyzed. Comparison with results of ab initio calculations revealed in general excellent agreement.