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Title: Systematic theoretical investigation of the zero-field splitting in Gd(III) complexes: Wave function and density functional approaches

The zero-field splitting (ZFS) of the electronic ground state in paramagnetic ions is a sensitive probe of the variations in the electronic and molecular structure with an impact on fields ranging from fundamental physical chemistry to medical applications. A detailed analysis of the ZFS in a series of symmetric Gd(III) complexes is presented in order to establish the applicability and accuracy of computational methods using multiconfigurational complete-active-space self-consistent field wave functions and of density functional theory calculations. The various computational schemes are then applied to larger complexes Gd(III)DOTA(H{sub 2}O){sup −}, Gd(III)DTPA(H{sub 2}O){sup 2−}, and Gd(III)(H{sub 2}O){sub 8}{sup 3+} in order to analyze how the theoretical results compare to experimentally derived parameters. In contrast to approximations based on density functional theory, the multiconfigurational methods produce results for the ZFS of Gd(III) complexes on the correct order of magnitude.
Authors:
;  [1] ;  [2] ;  [3] ;  [4]
  1. Department of Physics, Stockholm University, AlbaNova University Center, S-106 91 Stockholm (Sweden)
  2. Institute of Physics, Jagiellonian University, ul. Reymonta 4, PL-30-059 Krakow (Poland)
  3. Faculty of Mathematics and Computer Science, University of Warmia and Mazury in Olsztyn, Sloneczna 54, Olsztyn PL-10710 (Poland)
  4. Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm (Sweden)
Publication Date:
OSTI Identifier:
22416012
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 3; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; APPROXIMATIONS; COMPARATIVE EVALUATIONS; DENSITY FUNCTIONAL METHOD; DTPA; GADOLINIUM COMPLEXES; GROUND STATES; IONS; MOLECULAR STRUCTURE; PARAMAGNETISM; PHYSICAL CHEMISTRY; SELF-CONSISTENT FIELD; WATER; WAVE FUNCTIONS