6s and 4f ionized states of lanthanide calculated by the configuration-interaction method
Abstract
We have investigated the 6s and 4f ionized states of the whole lanthanide series. It is shown that the calculated 6s ionization energies (IE's) agree with experimental IE's within an error of 0.6 eV, if we add the relativistic correction to those given by configuration-interaction (CI) calculations; 6s IE's by CI calculations with the relativistic correction are in the range of 5.75 (La) to 6.29 eV (Lu); those by experiment are in 5.81 (La) to 6.89 eV (Lu). The relativistic effects reduce 4f IE's by 2-7 eV, and the correlation effects increase those by 1-2 eV for the light lanthanides and by 2-3 eV for the heavy lanthanides. The 4f IE's obtained by CI calculations with the relativistic correction agree with experiment, the error being of ~2 eV throughout the whole lanthanide series. Brewer [J. Opt. Soc. Am. 61, 1666 (1971)] estimated or assigned 4f ionized states experimentally with the electronic configuration of 4fm-15dn6s2 (n=1 for Ce+, Gd+, and Lu+, and n=0 for others). However, for some atoms such as Pr+, Nd+, Pm+, Sm+, and Gd+ we failed to obtain the ionized states having 4fm-15dn6s2 as the main configuration.
- Publication:
-
Physical Review A
- Pub Date:
- October 1997
- DOI:
- 10.1103/PhysRevA.56.2731
- Bibcode:
- 1997PhRvA..56.2731S
- Keywords:
-
- 31.30.Jv;
- Relativistic and quantum electrodynamic effects in atoms and molecules