Abstract

Biorthogonal perturbation methods originally developed for lanthanide crystal-field calculations are applied to 4f-4f electric dipole transition intensities for the system Pr3+-Cl-. The results confirm earlier suggestions that ligand polarization contributions are crucial to understanding the relative signs of the intensity parameters. They also show that ‘covalent’ or ‘charge transfer’ excitations from occupied ligand states to 4f orbitals give significant contributions. Our calculations are also applied to two-photon absorption and electronic Raman scattering amplitudes. The major second-order contribution to these processes comes from excitations from 4f to 5d orbitals.

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.