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Microwave Spectrum of the PD2Radical in the2B1Ground Electronic State

✍ Scribed by Tsuyoshi Hirao; Shin-ichi Hayakashi; Satoshi Yamamoto; Shuji Saito

Publisher: Elsevier Science
Year: 1998
Tongue: English
Weight: 317 KB
Volume: 187
Category: Article
ISSN: 0022-2852
DOI: 10.1006/jmsp.1997.7457

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✦ Synopsis

The rotational spectrum of the PD 2 radical in the 2 B 1 ground electronic state was observed in the region 165-463 GHz using a source-modulated microwave spectrometer. The PD 2 radical was generated in a free-space absorption cell by a dc glow discharge of D 2 over red phosphorus grains which were placed in the middle of the Pyrex glass cell. One hundred thirty fine and hyperfine components of 20 b-type rotational transitions were measured and analyzed by leastsquares methods. The rotational and centrifugal distortion constants, the spin-rotation coupling constants with their centrifugal distortion terms, and the hyperfine coupling constants of both the phosphorus and the deuterium nuclei were precisely determined. The phosphorus nuclear spin-rotation coupling constants were found to have relatively large values: C aa (P) Å 0.4815(89) MHz, C bb (P) Å 0.2501 (104) MHz, and C cc (P) Å 0.0564 (74) MHz, as suggested from those of PH 2 . The harmonic force field of PH 2 was derived from centrifugal distortion constants, inertial defects, and the reported vibrational frequencies for PH 2 and PD 2 . The determined force field was used to make harmonic corrections to the observed moments of inertia, and the r z structures for both species were derived, PH 2 : r z (PH) Å 1.43365(23) A ˚, u z (HPH) Å 91.622(32)Њ and PD 2 : r z (PD) Å 1.42852(17) A ˚, u z (DPD) Å 91.646(23)Њ,

where errors in parentheses are due to residual inertial defects of the corrected moments of inertia.

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