Resonance Raman spectra of metal halide vapor complexes

Conference · Sun Jan 01 04:00:00 EST 1978

OSTI ID:6515115

Paptheodorou, G N

Resonance Raman spectra of complex vapor phase compounds formed by reacting ''acidic'' gases (A/sub 2/X/sub 6/ = Al/sub 2/Cl/sub 6/, Al/sub 2/Br/sub 6/, In/sub 2/Cl/sub 6/) with metal halides have been measured. Spectra obtained from equilibrium vapor mixtures of A/sub 2/X/sub 6/ over solid MX/sub 2/ (= PdCl/sub 2/, PdBr/sub 2/, CuCl/sub 2/, CoBr/sub 2/, TiCl/sub 2/, FeCl/sub 2/, NiCl/sub 2/, PtCl/sub 2/) were a superposition of the A/sub 2/X/sub 6/-AX/sub 3/ bands and in few cases of new resonance-enhanced polarized bands due to MA/sub 2/X/sub 8/ and/or MAX/sub 5/ complexes. At temperatures above 800/sup 0/K, characteristic bands due to MX/sub 2/(g) (M = Fe, Co, Ni, Cu, Zn) and M/sub 2/X/sub 4/(g) (M = Cu) were observed. The predominant features of the PdAl/sub 2/Cl/sub 8/, CuAl/sub 2/Cl/sub 8/, and PdAl/sub 2/Br/sub 6/ spectra were three high-intensity, polarized bands which were attributed to the vibrational modes of the complex coupled to the electronic state of the central atom. The spectra of CuAlCl/sub 5/(g), CuInCl/sub 5/(g) and Cu/sub 2/Cl/sub 4/(g) species showed resonance enhancement of selective fundamentals which were attributed to vibrational modes of trigonally coordinated Cu(II). Resonance Raman spectra of U/sub 2/Cl/sub 10/(g) and UCl/sub 5/.AlCl/sub 3/(g) were characterized by the presence of a strong band attributed to the U-Cl/sub t/ stretching frequency. Raman band intensity measurements were carried out for the iron(III) chloride vapors and for the vapor complexes of CuAl/sub 2/Cl/sub 8/, CuInCl/sub 5/ and UCl/sub 5/.AlCl/sub 3/ using different laser powers and frequencies. The measurements suggested increasing spectroscopic temperatures and decomposition of the vapor complexes. The data are discussed in terms of the distribution of vibrational modes and the structure of the vapor species. 22 figs.

• Research Organization: Argonne National Lab., IL (USA)
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6515115
• Report Number(s): CONF-780941-8
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTINIDE COMPOUNDS
ALUMINIUM BROMIDES
ALUMINIUM CHLORIDES
ALUMINIUM COMPOUNDS
BROMIDES
BROMINE COMPOUNDS
CHLORIDES
CHLORINE COMPOUNDS
COBALT BROMIDES
COBALT COMPOUNDS
COMPLEXES
COPPER CHLORIDES
COPPER COMPOUNDS
COPPER HALIDES
ENERGY LEVELS
EXCITED STATES
FLUIDS
GASES
HALIDES
HALOGEN COMPOUNDS
INDIUM CHLORIDES
INDIUM COMPOUNDS
IRON CHLORIDES
IRON COMPOUNDS
NICKEL CHLORIDES
NICKEL COMPOUNDS
PALLADIUM BROMIDES
PALLADIUM CHLORIDES
PALLADIUM COMPOUNDS
PLATINUM CHLORIDES
PLATINUM COMPOUNDS
RAMAN SPECTRA
RESONANCE
SPECTRA
TITANIUM CHLORIDES
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
URANIUM CHLORIDES
URANIUM COMPOUNDS
VAPORS
VIBRATIONAL STATES