Derivation of Lanthanide Series Crystal Field Parameters From First Principles.

doi:10.1002/chem.201903141

This content will become publicly available on September 9, 2020

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

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Abstract

Two series of lanthanide complexes were chosen to analyze the trends of the magnetic properties along the series: the highly symmetric LnZn ₁₆(picHA) ₁₆ series with Ln = Tb, Dy, Ho, Er, Yb and picHA=picoline hydroxamic, and the [Ln(DPA) ₃](C ₃H ₅N ₂) ₃ · 3H ₂O 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.

Authors:

^[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

Publication Date:: 2019-09-09

Research Org.:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

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

OSTI Identifier:: 1566113

Report Number(s):: LA-UR-19-23436
Journal ID: ISSN 0947-6539

Grant/Contract Number:: 89233218CNA000001

Resource Type:: Accepted Manuscript

Journal Name:: Chemistry - A European Journal

Additional Journal Information:: Journal Volume: none; Journal Issue: none; Journal ID: ISSN 0947-6539

Publisher:: ChemPubSoc Europe

Country of Publication:: United States

Language:: English

Citation Formats


                    Jung, Julie Cathy Antoinette Odile, Islam, Md. Ashraful, Pecoraro, Vincent L., Mallah, Talal, Berthon, Claude, and Bolvin, Helene. Derivation of Lanthanide Series Crystal Field Parameters From First Principles..  United States: N. p., 2019. 
        Web.  doi:10.1002/chem.201903141.

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                    Jung, Julie Cathy Antoinette Odile, Islam, Md. Ashraful, Pecoraro, Vincent L., Mallah, Talal, Berthon, Claude, & Bolvin, Helene. Derivation of Lanthanide Series Crystal Field Parameters From First Principles..  United States.  doi:10.1002/chem.201903141.

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                    Jung, Julie Cathy Antoinette Odile, Islam, Md. Ashraful, Pecoraro, Vincent L., Mallah, Talal, Berthon, Claude, and Bolvin, Helene. Mon .  
        "Derivation of Lanthanide Series Crystal Field Parameters From First Principles.".  United States.  doi:10.1002/chem.201903141.

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@article{osti_1566113,

  title        = {Derivation of Lanthanide Series Crystal Field Parameters From First Principles.},

  author       = {Jung, Julie Cathy Antoinette Odile and Islam, Md. Ashraful and Pecoraro, Vincent L. and Mallah, Talal and Berthon, Claude and Bolvin, Helene},

  abstractNote = {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.},

  doi          = {10.1002/chem.201903141},

  journal      = {Chemistry - A European Journal},

  number       = none,

  volume       = none,

  place        = {United States},

  year         = {2019},

  month        = {9}

}

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