Resonance Raman spectra of inorganic salt vapors I. Palladium (II) and Copper(II) chloroaluminates

Journal Article · Fri Sep 01 04:00:00 EDT 1978 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.436805· OSTI ID:7049927

Papatheodorou, G N; Capote, M A

Resonance Raman spectra of vapor molecules formed by reacting gaseous aluminum chloride with solid PdCl/sub 2/ and CuCl/sub 2/ have been measured in the temperature range from 500 to 900 K and at total pressures up to 30 atm. The main features of the Raman spectra of the Pd--Al--Cl gaseous molecule are three polarized bands at 298, 176, and 84.5 cm/sup -1/. The excitation profiles of these bands exhibit minima in the vicinity of the maximum Pd(II) ligand field absorption, thus suggesting the presence of a center of symmetry in the molecule. A D/sub 2h/ molecular symmetry is proposed for the PdAl/sub 2/Cl/sub 8/ vapor complex having Pd(II) as a central atom in square planar coordination. The Raman spectra of the Cu--Al--Cl vapors are interpreted to account for two different molecular species. Three polarized bands at 281, 174.5, and 84.5 cm/sup -1/ are assigned to preresonance enhanced A/sub 1/ fundamentals of the CuAl/sub 2/Cl/sub 8/ molecule. Two strong bands at 448 and 291.5 cm/sup -1/ and their combinations and ovetones are assigned to resonance enhanced A/sub 1/ fundamentals of the CuAlCl/sub 5/ molecule having the Cu(II) in a trigonal coordination. Raman band intensity measurements using different laser line intensities suggest an increasing spectroscopic temperature and decomposition of the complex: CuAl/sub 2/Cl/sub 8/(g) ..-->..CuAlCl/sub 5/(g)+AlCl/sub 3/(g).

• Research Organization: Chemical Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439
• OSTI ID: 7049927
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 69:5; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ALUMINATES
ALUMINIUM COMPOUNDS
CHLORINE COMPOUNDS
COPPER COMPOUNDS
ENERGY LEVELS
HALOGEN COMPOUNDS
OXYGEN COMPOUNDS
PALLADIUM COMPOUNDS
RAMAN SPECTRA
SPECTRA
TRANSITION ELEMENT COMPOUNDS