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Ground-state splitting of [ital S]-state ion Cm[sup 3+] in LaCl[sub 3]

Journal Article · · Journal of Chemical Physics; (United States)
DOI:https://doi.org/10.1063/1.465139· OSTI ID:6299863
;  [1];  [2]
  1. Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)
  2. Department of Physics and Astronomy, University of Wisconsin at Eau Claire, Eau Claire, Wisconsin 54702 (United States)

We report optical-spectroscopic studies of the ground-state splitting of the nominal [ital S]-state ion Cm[sup 3+] in LaCl[sub 3]. A total splitting of 1.97[plus minus]0.05 cm[sup [minus]1] for the [sup 8]S[sub 7/2] ground state of this system has been measured for the first time. Both electric and magnetic dipole transitions were observed. Energy levels of all four Kramers doublets of the [sup 8]S[sub 7/2] manifold were resolved by means of the site-selective excitation and emission spectra of [sup 8]S[sub 7/2][leftrightarrow][sup 6]D[sub 7/2] and [sup 8]S[sub 7/2][leftrightarrow][sup 6]P[sub 5/2] transitions. Our results show that the lowest component of the ground manifold is a [mu]=5/2 state dominated by [ital M]=[vert bar][plus minus]7/2[r angle] in contrast to a previously reported [mu]=1/2 state. The crystal-field model, established through analyzing optical spectra of the excited states, predicts a ground-state splitting with the right ordering but greater magnitude. In comparison with the lanthanide [ital S]-state ion Gd[sup 3+], much stronger spin--orbit coupling and reduced electrostatic interaction in concert with greater crystal field interaction significantly influence the characteristics of the ground state of the actinide [ital S]-state ion. Contributions from within the 5[ital f][sup 7] configuration account for most of the observed splitting.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
6299863
Journal Information:
Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 99:5; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English