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High Resolution FTIR Study of PF3in the 800–950 cm−1Region. The ν1and ν3Fundamental and ν2+ ν4Combination Bands

✍ Scribed by N.Ben Sari-Zizi; H. Bürger; M. Litz; H. Najib; J. Radtke

Publisher
Elsevier Science
Year
1996
Tongue
English
Weight
376 KB
Volume
177
Category
Article
ISSN
0022-2852

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✦ Synopsis

The FTIR spectrum of PF 3 has been recorded in the 750-950 cm 01 range covering the fundamentals n 1 (891.940 5 cm 01 ) and n 3 (859.544 1 cm 01 ) and the combination band n 2 / n 4 (834.055 7 cm 01 ) with a resolution of ca. 2.5 1 10 03 cm 01 . Furthermore, spectra of the 2n 2 , 2n 2 0 n 2 , (n 2 / n 4 ) 0 n 4 , and (n 2 / n 4 ) 0 n 2 bands were measured and analyzed. The vibrotational analysis of the n 1 and n 3 bands confirmed the presence of a Coriolis x, y resonance whose interaction parameter could be determined experimentally. A transition moment ratio m 1 :m 3 close to 0.7 has been deduced from a band contour simulation for a negative sign of the intensity perturbation m 1 z 1,3 m 3 . Furthermore, anharmonic resonance between n 3 and n 2 / n 4 was established, the strength of which is in agreement with an interaction constant W 234 Å 2.86 cm 01 as suggested by ab initio calculations. More than 5000 rovibrational transitions belonging to n 1 , n 3 , and n 2 / n 4 were fitted together with all available pure rotational data, s(Fit) of the IR data being 3.93 1 10 04 cm 01 . It was found that q resonance within n 3 induces an avoided crossing of the kᐉ Å 1, A 0 with the kᐉ Å 02, A 0 sublevel near J Å 12. Its effects give rise to an irregular A 1 A 2 splitting of P (PQR) 3 lines and the R Q 0 branch near the crossing. The equilibrium rotational constants B e and C e have been determined, and their significance is critically assessed. An equilibrium structure, d e (PF) Å 1.560 99(14) A ˚and ЄFPF 97.57(4)Њ, has been calculated.

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