The Raman Spectrum of Arsenic Trifluoride and the Molecular Constants of AsF3, AsCl3 and PCl3

Abstract

The Raman spectrum of AsF3 was found to consist of four lines with the frequencies ω1(1), 707; ω2(1), 341; ω3(2), 644; and ω4(2), 274 cm—1. The selection rules require a pyramidal molecule. Electron diffraction data for AsF3, AsCl3 and PCl3 are used to establish the bond angles. The entropies of the three trihalides were calculated, and the standard free energies of formation of AsCl3(l) and AsCl3(g) were determined to be —65,190 cal. and —62,718 cal., respectively, at 25°.

Ca(AsF3)(AsF6)2: the first alkaline earth metal cation coordinated to AsF3

“…KrF + salts) [17]. All strong bands in the Raman spectrum of Ca(AsF 3 )(AsF 6 ) 2 could be assigned to the nAsF 3 (737 (7), 715(50), 649(10), 364 (20) and 288(2) cm À1 ) and nAsF 6 À vibrational modes (763(2), 699(100), 588 (13), 544(15) and 379(18) cm À1 ) (numbers in parentheses denote relative intensities).…”

“…4) were tentatively assigned by comparison with the Raman spectra of similar compounds. Vibrational bands in the Raman spectrum of neutral AsF 3 (vapour phase) appear at 739(n 1 ), 337(n 2 ), 699(n 3 ) and 274(n 4 ) cm À1 [12], while AsF 3 in the liquid phase has the following vibrations: n 1 707, n 2 341, n 3 644 and n 4 274 cm À1 [13]. The vibrations of the regular AsF 4 À anion in CsAsF 4 are at 659, 592, 447, 397, 377, 354, 325 and 311 cm À1 [14] while the vibrations of the cation AsF 2 + in AsF 3 .SbF 5 are at 738(n 1 ) and 728 cm À1 and, possibly, at 700(n 3 ) cm À1 [15].…”

Quantitative photoabsorption and fluorescence spectroscopy of AsF3in the vacuum ultraviolet

“…The trivalent group V halides are of great interest in theoretical chemistry (Gillespie 1960). AsF, has been extensively studied in vibrational frequencies and force constants (Yost and Sherborne 1934, Hoskins and Lord 1965, Levin and Abramowitz 1966, Hoskins 1966, Mirri 1967, Reichman et a1 1970 as well as in molecular structure (Kisliuk and Geschwind 1953, Clippard and Bartell 1970, Konaka and Kimura 1970, Konaka 1970. The photoelectron spectra of AsF, were reported by Potts et al (1970) and Grodzicki er a1 (1984).…”