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

Abstract

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.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5];  [2]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Laboratoire de Chimie et Physique Quantiques, CNRS, Universite Toulouse III, Toulouse (France)
  3. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry
  4. Universite de Paris, Orsay Cedex (France). Institut de Chimie Moleculaire et des Materiaux d’Orsay, CNRS
  5. Radiochemistry Pro- cesses Department, DRCP, Bagnols sur Ceze, (France). Nuclear Energy Division
Publication Date:
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
Alternate Identifier(s):
OSTI ID: 1572418
Report Number(s):
LA-UR-19-23436
Journal ID: ISSN 0947-6539; TRN: US2000972
Grant/Contract Number:  
89233218CNA000001; 89233218NCA000001
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
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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.
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.
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. https://www.osti.gov/servlets/purl/1566113.
@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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Works referenced in this record:

Matrix Elements and Operator Equivalents Connected with the Magnetic Properties of Rare Earth Ions
journal, March 1952


Magnetic properties of a fourfold degenerate state: Np4+ ion diluted in Cs2ZrCl6 crystal
journal, June 2014

  • Hernández, Dayán Páez; Bolvin, Hélène
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 194
  • DOI: 10.1016/j.elspec.2014.03.002

What Use Are Crystal Field Parameters? A Chemist’s Viewpoint
journal, May 2010

  • Duan, Chang-Kui; Tanner, Peter A.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 19
  • DOI: 10.1021/jp1015214

The Douglas–Kroll–Hess Approach
journal, June 2011

  • Nakajima, Takahito; Hirao, Kimihiko
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr200040s

Covalency in f-element bonds
journal, October 2002


Determination of Ligand-Field Parameters and f-Electronic Structures of Double-Decker Bis(phthalocyaninato)lanthanide Complexes
journal, April 2003

  • Ishikawa, Naoto; Sugita, Miki; Okubo, Tomoko
  • Inorganic Chemistry, Vol. 42, Issue 7
  • DOI: 10.1021/ic026295u

Nuclear magnetic resonance shifts in solution due to lanthanide ions
journal, September 1972


PHI: A powerful new program for the analysis of anisotropic monomeric and exchange-coupled polynuclear d - and f -block complexes
journal, February 2013

  • Chilton, Nicholas F.; Anderson, Russell P.; Turner, Lincoln D.
  • Journal of Computational Chemistry, Vol. 34, Issue 13
  • DOI: 10.1002/jcc.23234

The raising of angular momentum degeneracy of f-Electron terms by cubic crystal fields
journal, October 1962


Improved Segmented All-Electron Relativistically Contracted Basis Sets for the Lanthanides
journal, February 2016

  • Aravena, Daniel; Neese, Frank; Pantazis, Dimitrios A.
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 3
  • DOI: 10.1021/acs.jctc.5b01048

Strategies towards single molecule magnets based on lanthanide ions
journal, October 2009


An improvement of the resolution of the identity approximation for the formation of the Coulomb matrix
journal, September 2003

  • Neese, Frank
  • Journal of Computational Chemistry, Vol. 24, Issue 14
  • DOI: 10.1002/jcc.10318

An electrostatic model for the determination of magnetic anisotropy in dysprosium complexes
journal, October 2013

  • Chilton, Nicholas F.; Collison, David; McInnes, Eric J. L.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3551

Periodic Trends in Lanthanide Compounds through the Eyes of Multireference ab Initio Theory
journal, April 2016


Interplay between Local Anisotropies in Binuclear Complexes
journal, April 2014

  • Ruamps, Renaud; Maurice, Rémi; de Graaf, Coen
  • Inorganic Chemistry, Vol. 53, Issue 9
  • DOI: 10.1021/ic500180k

Covalency in f-element complexes
journal, January 2013

  • Neidig, Michael L.; Clark, David L.; Martin, Richard L.
  • Coordination Chemistry Reviews, Vol. 257, Issue 2
  • DOI: 10.1016/j.ccr.2012.04.029

Gaussian basis sets of quadruple zeta valence quality for atoms H–Kr
journal, December 2003

  • Weigend, Florian; Furche, Filipp; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 119, Issue 24
  • DOI: 10.1063/1.1627293

Douglas–Kroll–Hess Theory: a relativistic electrons-only theory for chemistry
journal, January 2006


Elucidating the Magnetic Anisotropy and Relaxation Dynamics of Low-Coordinate Lanthanide Compounds
journal, January 2016


A mean-field spin-orbit method applicable to correlated wavefunctions
journal, March 1996


Optical spectra, energy levels, and crystal‐field analysis of tripositive rare earth ions in Y 2 O 3 . I. Kramers ions in C 2 sites
journal, April 1982

  • Chang, N. C.; Gruber, John B.; Leavitt, Richard P.
  • The Journal of Chemical Physics, Vol. 76, Issue 8
  • DOI: 10.1063/1.443530

Crystal Field in Rare-Earth Complexes: From Electrostatics to Bonding
journal, March 2018

  • Alessandri, Riccardo; Zulfikri, Habiburrahman; Autschbach, Jochen
  • Chemistry - A European Journal, Vol. 24, Issue 21
  • DOI: 10.1002/chem.201705748

Structure and thermodynamics of lanthanide and actinide complexes in solution
journal, January 1971


Ab initio calculation of anisotropic magnetic properties of complexes. I. Unique definition of pseudospin Hamiltonians and their derivation
journal, August 2012

  • Chibotaru, L. F.; Ungur, L.
  • The Journal of Chemical Physics, Vol. 137, Issue 6
  • DOI: 10.1063/1.4739763

Computerized magnetic studies on d, f, d–d, f–f, and d–S, f–S systems under varying ligand and magnetic fields
journal, October 2004


Local properties of quantum chemical systems: The LoProp approach
journal, September 2004

  • Gagliardi, Laura; Lindh, Roland; Karlström, Gunnar
  • The Journal of Chemical Physics, Vol. 121, Issue 10
  • DOI: 10.1063/1.1778131

Valence Strength and the Magnetism of Complex Salts
journal, December 1935

  • Van Vleck, J. H.
  • The Journal of Chemical Physics, Vol. 3, Issue 12
  • DOI: 10.1063/1.1749596

Rationalization of Anomalous Pseudocontact Shifts and Their Solvent Dependence in a Series of C 3 -Symmetric Lanthanide Complexes
journal, September 2017

  • Vonci, Michele; Mason, Kevin; Suturina, Elizaveta A.
  • Journal of the American Chemical Society, Vol. 139, Issue 40
  • DOI: 10.1021/jacs.7b07094

Theory of Complex Spectra. IV
journal, November 1949


Molecular Anisotropy Analysis of Single-Ion Magnets Using an Effective Electrostatic Model
journal, September 2014

  • Baldoví, José J.; Clemente-Juan, Juan M.; Coronado, Eugenio
  • Inorganic Chemistry, Vol. 53, Issue 20
  • DOI: 10.1021/ic5020253

First principles approach to the electronic structure, magnetic anisotropy and spin relaxation in mononuclear 3d-transition metal single molecule magnets
journal, April 2015

  • Atanasov, Mihail; Aravena, Daniel; Suturina, Elizaveta
  • Coordination Chemistry Reviews, Vol. 289-290
  • DOI: 10.1016/j.ccr.2014.10.015

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980


MOLCAS 7: The Next Generation
journal, January 2010

  • Aquilante, Francesco; De Vico, Luca; Ferré, Nicolas
  • Journal of Computational Chemistry, Vol. 31, Issue 1
  • DOI: 10.1002/jcc.21318

The restricted active space (RAS) state interaction approach with spin–orbit coupling
journal, May 2002


Modeling the properties of lanthanoid single-ion magnets using an effective point-charge approach
journal, January 2012

  • Baldoví, José J.; Borrás-Almenar, Juan J.; Clemente-Juan, Juan M.
  • Dalton Transactions, Vol. 41, Issue 44
  • DOI: 10.1039/c2dt31411h

Near-Infrared Optical Imaging of Necrotic Cells by Photostable Lanthanide-Based Metallacrowns
journal, June 2017

  • Martinić, Ivana; Eliseeva, Svetlana V.; Nguyen, Tu N.
  • Journal of the American Chemical Society, Vol. 139, Issue 25
  • DOI: 10.1021/jacs.7b01587

Universal Theoretical Approach to Extract Anisotropic Spin Hamiltonians
journal, October 2009

  • Maurice, Rémi; Bastardis, Roland; Graaf, Coen de
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 11
  • DOI: 10.1021/ct900326e

Assembly of Near-Infrared Luminescent Lanthanide Host(Host-Guest) Complexes With a Metallacrown Sandwich Motif
journal, September 2011

  • Jankolovits, Joseph; Andolina, Christopher M.; Kampf, Jeff W.
  • Angewandte Chemie International Edition, Vol. 50, Issue 41
  • DOI: 10.1002/anie.201103851

Unique Definition of the Zeeman-Splitting g Tensor of a Kramers Doublet
journal, July 2008


Spectroscopic Properties of Rare Earths
journal, September 1965

  • Wybourne, Brian G.; Meggers, William F.
  • Physics Today, Vol. 18, Issue 9
  • DOI: 10.1063/1.3047727

Exploiting single-ion anisotropy in the design of f-element single-molecule magnets
journal, January 2011

  • Rinehart, Jeffrey D.; Long, Jeffrey R.
  • Chemical Science, Vol. 2, Issue 11
  • DOI: 10.1039/c1sc00513h

Structure-independent method for dissecting contact and dipolar NMR shifts in lanthanide complexes and its use in structure determination
journal, November 1975

  • Reilley, Charles N.; Good, B. W.; Desreux, J. F.
  • Analytical Chemistry, Vol. 47, Issue 13
  • DOI: 10.1021/ac60363a011

Software update: the ORCA program system, version 4.0: Software update
journal, July 2017

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1
  • DOI: 10.1002/wcms.1327

Ab Initio Crystal Field for Lanthanides
journal, February 2017

  • Ungur, Liviu; Chibotaru, Liviu F.
  • Chemistry - A European Journal, Vol. 23, Issue 15
  • DOI: 10.1002/chem.201605102

Ab initio direct calculation of the singlet-triplet separation in cupric acetate hydrate dimer
journal, July 1981

  • De Loth, P.; Cassoux, P.; Daudey, J. P.
  • Journal of the American Chemical Society, Vol. 103, Issue 14
  • DOI: 10.1021/ja00404a007

A theoretical analysis of chemical bonding, vibronic coupling, and magnetic anisotropy in linear iron( ii ) complexes with single-molecule magnet behavior
journal, January 2013

  • Atanasov, Mihail; Zadrozny, Joseph M.; Long, Jeffrey R.
  • Chem. Sci., Vol. 4, Issue 1
  • DOI: 10.1039/C2SC21394J

An Alternative Approach to the g-Matrix: Theory and Applications
journal, June 2006


Magnetic Coupling in the Ce(III) Dimer Ce 2 (COT) 3
journal, December 2018


Unraveling σ and π Effects on Magnetic Anisotropy in cis -NiA 4 B 2 Complexes: Magnetization, HF-HFEPR Studies, First-Principles Calculations, and Orbital Modeling
journal, October 2016

  • Charron, Gaëlle; Malkin, Elena; Rogez, Guillaume
  • Chemistry - A European Journal, Vol. 22, Issue 47
  • DOI: 10.1002/chem.201602837

Optical and magnetic properties of the 5f[sup 1]AnX[sub 6][sup q−] series: A theoretical study
journal, January 2009

  • Notter, François-Paul; Bolvin, Hélène
  • The Journal of Chemical Physics, Vol. 130, Issue 18
  • DOI: 10.1063/1.3124193

Automatic Generation of Auxiliary Basis Sets
journal, January 2017

  • Stoychev, Georgi L.; Auer, Alexander A.; Neese, Frank
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 2
  • DOI: 10.1021/acs.jctc.6b01041

Insight of the Metal–Ligand Interaction in f‐Element Complexes by Paramagnetic NMR Spectroscopy
journal, February 2019

  • Autillo, Matthieu; Guerin, Laetitia; Dumas, Thomas
  • Chemistry – A European Journal, Vol. 25, Issue 17
  • DOI: 10.1002/chem.201805858

NMR chemical shift as analytical derivative of the Helmholtz free energy
journal, February 2013

  • Van den Heuvel, Willem; Soncini, Alessandro
  • The Journal of Chemical Physics, Vol. 138, Issue 5
  • DOI: 10.1063/1.4789398

Assembly of Near-Infrared Luminescent Lanthanide Host(Host-Guest) Complexes With a Metallacrown Sandwich Motif
journal, September 2011

  • Jankolovits, Joseph; Andolina, Christopher M.; Kampf, Jeff W.
  • Angewandte Chemie, Vol. 123, Issue 41
  • DOI: 10.1002/ange.201103851

Termaufspaltung in Kristallen
journal, January 1929


Magnetic Slow Relaxation in a Metal-Organic Framework Made of Chains of Ferromagnetically Coupled Single-Molecule Magnets
journal, March 2018

  • Huang, Gang; Fernandez-Garcia, Guglielmo; Badiane, Insa
  • Chemistry - A European Journal, Vol. 24, Issue 27
  • DOI: 10.1002/chem.201800095

Ab Initio Ligand-Field Theory Analysis and Covalency Trends in Actinide and Lanthanide Free Ions and Octahedral Complexes
journal, July 2017


Ab initio model potential embedded‐cluster study of V 2+ ‐doped fluoroperovskites: Effects of different hosts on the local distortion and electronic structure of 4 T 2 g 4 A 2 g laser levels
journal, August 1995

  • López‐Moraza, Sara; Pascual, José Luis; Barandiarán, Zoila
  • The Journal of Chemical Physics, Vol. 103, Issue 6
  • DOI: 10.1063/1.469688

The lanthanide crystal field in cubic Cs 2 NaLnCl 6 elpasolites
journal, August 1980

  • Faulkner, Thomas R.; Morley, John P.; Richardson, Frederick S.
  • Molecular Physics, Vol. 40, Issue 6
  • DOI: 10.1080/00268978000102421

    Works referencing / citing this record:

    Crystallographic structure and crystal field parameters in the [An IV (DPA) 3 ] 2− series, An = Th, U, Np, Pu
    journal, January 2020

    • Autillo, Matthieu; Islam, Md. Ashraful; Jung, Julie
    • Physical Chemistry Chemical Physics, Vol. 22, Issue 25
    • DOI: 10.1039/d0cp02137g