The ν1 and ν3 stretching fundamental bands of PD3

✍ Scribed by E. Canè; L. Fusina; W. Jerzembeck; H. Bürger

• Publisher: Elsevier Science
• Year: 2003
• Tongue: English
• Weight: 204 KB
• Volume: 220
• Category: Article
• ISSN: 0022-2852
• DOI: 10.1016/s0022-2852(03)00122-x

✦ Synopsis

The infrared (IR) spectrum of PD 3 has been recorded in the 1580-1800 cm À1 range at a resolution of 0.0027 cm À1 . About 2400 rovibrational transitions with J 0 ¼ K 0 6 22 have been measured and assigned to the m 1 (A 1 ) and m 3 (E) stretching fundamentals. These include 506 ''perturbation-allowed'' transitions with selection rules Dðk À lÞ ¼ AE3. Splittings of the K 00 ¼ 3 lines have been observed. Effects of strong perturbations are evident in the spectrum. Therefore the rovibrational Hamiltonian adopted for the analysis explicitly takes into account the Coriolis and k-type interactions between the v 1 ¼ 1 and v 3 ¼ 1 states, and includes also several essential resonances within these states. The rotational structure in the v 1 ¼ 1 and v 3 ¼ 1 vibrational states up to J 0 ¼ K 0 ¼ 18 was reproduced by fitting simultaneously all experimental data. Thirty-four parameters reproduced 1950 transitions retained in the final cycle with a standard deviation of the fit equal to 4.9 Â 10 À4 cm À1 (about the precision of the experimental measurements).