2005/02/26 by Chang-Kui Duan, Chang‐Kui Duan, Michael F. Reid
Materials Science · Physics and Astronomy · #Advanced Chemical Physics Studies #Lanthanide and Transition Metal Complexes #Quantum optics and atomic interactions #cond-mat.mtrl-sci
paper · pdf · doi:10.1063/1.1855880
published as THE JOURNAL OF CHEMICAL PHYSICS 122, 094714 (2005) · 10 pages, 1 figure
openalex publication_date 2005/02/26 · arxiv created 2005/05/24 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
The 4f-5d transition rates for rare-earth ions in crystals can be calculated with an effective transition operator acting between model 4f(N) and 4f(N-1)5d states calculated with effective Hamiltonian, such as semiempirical crystal Hamiltonian. The difference of the effective transition operator from the original transition operator is the corrections due to mixing in transition initial and final states of excited configurations from both the center ion and the ligand ions. These corrections are calculated using many-body perturbation theory. For free ions, there are important one-body and two-body corrections. The one-body correction is proportional to the original electric dipole operator with magnitude of approximately 40% of the uncorrected electric dipole moment. Its effect is equivalent to scaling down the radial integral (5d/r/4f) to about 60% of the uncorrected HF value. The two-body correction has magnitude of approximately 25% relative to the uncorrected electric dipole moment. For ions in crystals, there is an additional one-body correction due to ligand polarization, whose magnitude is shown to be about 10% of the uncorrected electric dipole moment.