Derivation of Lanthanide Series Crystal Field Parameters From First Principles.

Jung, Julie Cathy Antoinette Odile; Islam, Md. Ashraful; Pecoraro, Vincent L.; Mallah, Talal; Berthon, Claude; Bolvin, Helene

doi:10.1002/chem.201903141

Title: Derivation of Lanthanide Series Crystal Field Parameters From First Principles.

Journal Article · 09 September 2019 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.201903141 · OSTI ID:1566113

^[1]; Islam, Md. Ashraful ^[2]; Pecoraro, Vincent L. ^[3]; Mallah, Talal ^[4]; Berthon, Claude ^[5]; Bolvin, Helene ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Laboratoire de Chimie et Physique Quantiques, CNRS, Universite Toulouse III, Toulouse (France)
Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry
Universite de Paris, Orsay Cedex (France). Institut de Chimie Moleculaire et des Materiaux d’Orsay, CNRS
Radiochemistry Pro- cesses Department, DRCP, Bagnols sur Ceze, (France). Nuclear Energy Division

Two series of lanthanide complexes were chosen to analyze the trends of the magnetic properties along the series: the highly symmetric LnZn₁₆(picHA)₁₆ series with Ln = Tb, Dy, Ho, Er, Yb and picHA=picoline hydroxamic, and the [Ln(DPA)₃](C₃H₅N₂)₃ · 3H₂O series with DPA = 2,6-dipicolinic acid and Ln = Ce–Yb and the approximate threefold symmetry. The first series present a compressed coordination sphere of 8 oxygen atoms environment while in the 2nd series, the coordination sphere is formed by an elongated coordination sphere formed by 6 oxygen atoms. Crystal field parameters (CFPs) are deduced from ab initio calculations using two methods: the AILFT (Ab Initio Ligand Field Theory) which determines the parameters at the orbital level, and the ITO (Irreducible Technique Operator) decomposition which treats the problem at the many-electron level. It is shown that the CFPs are transferable from one derivative to the other, within a given series. The sign of the 2nd order parameter $$B_0^2$$ differs in the two series reflecting the difference of environment. It is shown that the use of strength parameter $$S$$ permits a easy comparison between complexes. Furthermore, in both cases, the parameters are found to decrease in magnitude along the series and this decrease is imputed to covalent effects.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1566113

Report Number(s):: LA-UR-19-23436

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: none Vol. none; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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