Terbium chloride--aluminum chloride vapor system. III. Spectral intensity analysis

Journal Article · Sun Mar 15 04:00:00 EST 1981 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.441517· OSTI ID:6524433

Caird, J A; Carnall, W T; Hessler, J P

The intensities of Tb/sup 3 +/ ground state absorption and /sup 5/D/sub 4/ fluorescence transitions in the TbCl/sub 3/(AlCl/sub 3/)/sub x/(g) complex system have been analyzed according to the Judd--Ofelt theory of forced electric dipole transitions. This represents the first successful attempt to utilize observations of both absorption and fluorescence spectra in establishing the parameters of the theory. The positions of 19 Tb/sup 3 +/ energy levels were determined from the spectra and used to perform a parametric analysis of the Hamiltonian matrix for the ion's 4f/sup 8/ configuration. The wave functions obtained in diagonalization of the Hamiltonian were used to calculate unit tensor operator matrix elements required in the intensity analysis. A good fit to the measurements was obtained with intensity parameters ..cap omega../sub 2/=20.5, ..cap omega../sub 4/=2.3, and ..cap omega../sub 6/=3.0 pm/sup 2/. These results were then used to compute intensities of fluorescence transitions from the higher lying /sup 5/D/sub 3/, /sup 5/G/sub 6/, and /sup 5/L/sub 10/ levels, yielding additional qualitative agreement between theory and experiment. Some of the major discrepancies between theory and experiment may be due to the need for inclusion of odd-order intensity parameters or J mixing in the Judd--Ofelt theory.

• Research Organization: Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6524433
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 74:6; 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
ABSORPTION SPECTRA
ALUMINIUM CHLORIDES
ALUMINIUM COMPLEXES
ALUMINIUM COMPOUNDS
CHARGED PARTICLES
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
EMISSION SPECTRA
ENERGY-LEVEL TRANSITIONS
FLUIDS
FLUORESCENCE
GASES
HALIDES
HALOGEN COMPOUNDS
IONS
LUMINESCENCE
OSCILLATOR STRENGTHS
RARE EARTH COMPOUNDS
SPECTRA
TERBIUM CHLORIDES
TERBIUM COMPOUNDS
TERBIUM IONS
VAPORS