Title: X-ray absorption spectra of f-element complexes: insight from relativistic multiconfigurational wavefunction theory

Journal Article · · Dalton Transactions
DOI: https://doi.org/10.1039/d1dt04075h · OSTI ID:1978781
ORCiD logo [1]; ORCiD logo [1]
  1. University at Buffalo, State University of New York, NY (United States)
+ Show Author Affiliations

X-ray absorption near edge structure (XANES) spectroscopy, coupled with ab initio calculations, has emerged as the state-of-the-art tool for elucidating the metal-ligand bonding in f-element complexes. Furthermore, this highlight presents recent efforts in calculating XANES spectra of lanthanide and actinide compounds with relativistic multiconfiguration wavefunction approaches that account for differences in donation bonding in the ground state (GS) versus a core-excited state (ES), multiplet effects, and spin-orbit-coupling. With the GS and ES wavefunctions available, including spin-orbit effects, an arsenal of chemical bonding tools that are popular among chemists can be applied to rationalize the observed intensities in terms of covalent bonding.

Research Organization:
State University of New York (SUNY), Albany, NY (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001136
OSTI ID:
1978781
Journal Information:
Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 5 Vol. 51; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (164)

Performance of relativistic density functional and ab initio pseudopotential approaches for systems with high-spin multiplicities: Gadolinium diatomics GdX (X=H, N, O, F, P, S, Cl, Gd) journal January 2000
Relativistic and Electron-Correlation Effects in the Ground States of Lanthanocenes and Actinocenes journal February 1998
Reaching the Maximum Multiplicity of the Covalent Chemical Bond journal February 2007
Direct Observation of Molecular Orbital Mixing in a Solvated Organometallic Complex journal July 2013
Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides journal April 2016
A Novel Metastable Pentavalent Plutonium Solid Phase on the Pathway from Aqueous Plutonium(VI) to PuO 2 Nanoparticles journal December 2019
Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal-Field Models journal May 2014
Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States journal November 2019
Endohedral Metallofullerenes: New Structures and Unseen Phenomena journal March 2020
Probing Multiconfigurational States by Spectroscopy: The Cerium XAS L 3 ‐edge Puzzle journal March 2021
Development of Single‐Molecule Magnets † journal June 2020
Ionic bonding of lanthanides, as influenced by d- and f-atomic orbitals, by core-shells and by relativity journal January 2015
Cost and sensitivity of restricted active-space calculations of metal L-edge X-ray absorption spectra: Effects of the Active-Space Selection on the L-Edge XAS Spectra journal October 2015
Efficient optimization of natural resonance theory weightings and bond orders by gram‐based convex programming journal May 2019
Periodic trends and complexation chemistry of tetravalent actinide ions with a potential actinide decorporation agent 5‐LIO(Me‐3,2‐HOPO): A relativistic density functional theory exploration journal March 2020
Insight into the X‐ray absorption spectra of Cu‐porphyrazines from electronic structure theory journal October 2020
Simulating Cl K-edge X-ray absorption spectroscopy in MCl6 2− (M = U, Np, Pu) complexes and UOCl5 − using time-dependent density functional theory journal February 2014
Excitation energies in the nickel atom studied with the complete active space SCF method and second-order perturbation theory journal April 1992
Direct, atomic orbital, static exchange calculations of photoabsorption spectra of large molecules and clusters journal May 1994
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach journal May 1980
Formally tetravalent cerium and thorium compounds: a configuration interaction study of cerocene Ce(C8H8)2 and thorocene Th(C8H8)2 using energy-adjusted quasirelativistic ab initio pseudopotentials journal June 1995
L3 edge X-ray absorption spectrum of CeO2: crystal structure effects journal March 1995
The restricted active space (RAS) state interaction approach with spin–orbit coupling journal May 2002
The multi-state CASPT2 method journal May 1998
The He-I photoelectron spectra of uranocene and thorocene journal May 1976
Covalency in f-element complexes journal January 2013
Theoretical insights into the chemical bonding in actinide complexes journal May 2014
K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites journal August 2017
Solvation and speciation of cobalt(II). A theoretical X-ray absorption and RIXS study journal April 2020
Using singular value decomposition for a compact presentation and improved interpretation of the CIS wave functions journal April 2007
A new analysis of X-ray adsorption branching ratios: Use of Russell–Saunders coupling journal April 2008
Two interpretations of the cerocene electronic ground state journal February 2014
Delocalization and occupancy effects of 5f orbitals in plutonium intermetallics using L3-edge resonant X-ray emission spectroscopy journal June 2014
2p x-ray absorption spectroscopy of 3d transition metal systems journal May 2021
Investigation of actinide compounds by coupling X-ray absorption spectroscopy and quantum chemistry journal October 2007
The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges journal October 2010
Correlating Electronic Structure and Magnetic Anisotropy in Actinide Complexes [An(COT) 2 ], An III/IV = U, Np, and Pu journal May 2020
From π Bonds without σ Bonds to the Longest Metal–Metal Bond Ever: A Survey on Actinide–Actinide Bonding in Fullerenes journal August 2020
Computational and Spectroscopic Tools for the Detection of Bond Covalency in Pu(IV) Materials journal October 2021
Relativistic Multiconfigurational Ab Initio Calculation of Uranyl 3d4f Resonant Inelastic X-ray Scattering journal November 2021
Use of HERFD–XANES at the U L 3 - and M 4 -Edges To Determine the Uranium Valence State on [Ni(H 2 O) 4 ] 3 [U(OH,H 2 O)(UO 2 ) 8 O 12 (OH) 3 ] journal April 2016
Cerium Tetrakis(tropolonate) and Cerium Tetrakis(acetylacetonate) Are Not Diamagnetic but Temperature-Independent Paramagnets journal June 2018
Enhancing Actinide(III) over Lanthanide(III) Selectivity through Hard-by-Soft Donor Substitution: Exploitation and Implication of Near-Degeneracy-Driven Covalency journal July 2019
Competitive Reaction of Neptunium(V) and Uranium(VI) in Potassium–Sodium Carbonate-Rich Aqueous Media: Speciation Study with a Focus on High-Resolution X-ray Spectroscopy journal December 2019
Local Structure in U(IV) and U(V) Environments: The Case of U 3 O 7 journal March 2020
Spin–Orbit Natural Transition Orbitals and Spin-Forbidden Transitions journal November 2021
Near-Edge X-ray Absorption Fine Structure within Multilevel Coupled Cluster Theory journal May 2016
Impact of the Kohn–Sham Delocalization Error on the 4f Shell Localization and Population in Lanthanide Complexes journal June 2016
Ab Initio Wave Function-Based Determination of Element Specific Shifts for the Efficient Calculation of X-ray Absorption Spectra of Main Group Elements and First Row Transition Metals journal May 2018
Restricted Open-Shell Configuration Interaction Singles Study on M- and L-edge X-ray Absorption Spectroscopy of Solid Chemical Systems journal June 2018
New and Efficient Equation-of-Motion Coupled-Cluster Framework for Core-Excited and Core-Ionized States journal April 2019
OpenMolcas: From Source Code to Insight journal September 2019
Computational Study of Actinyl Ion Complexation with Dipyriamethyrin Macrocyclic Ligands journal January 2021
Unraveling the Electronic Structure of Photocatalytic Manganese Complexes by L-Edge X-ray Spectroscopy journal August 2015
Equation-of-Motion Coupled-Cluster Theory to Model L-Edge X-ray Absorption and Photoelectron Spectra journal September 2020
Ab Initio Study of Covalency in the Ground versus Core-Excited States and X-ray Absorption Spectra of Actinide Complexes journal September 2018
Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States journal September 2016
Ligand K-Edge X-ray Absorption Spectroscopy:  A Direct Probe of Ligand−Metal Covalency journal December 2000
The electronic structure of actinide-containing molecules: a challenge to applied quantum chemistry journal July 1991
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning journal June 2012
Homoleptic Cerium(III) and Cerium(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State journal September 2013
Oxo-Exchange of Gas-Phase Uranyl, Neptunyl, and Plutonyl with Water and Methanol journal December 2013
Magnetic Properties and Electronic Structures of Ar 3 U IV –L Complexes with Ar = C 5 (CH 3 ) 4 H – or C 5 H 5 – and L = CH 3 , NO, and Cl journal November 2014
The restricted active space self-consistent-field method, implemented with a split graph unitary group approach journal July 1990
Second-order perturbation theory with a CASSCF reference function journal July 1990
X-ray absorption spectroscopic studies of the blue copper site: metal and ligand K-edge studies to probe the origin of the EPR hyperfine splitting in plastocyanin journal January 1993
Ligand K-edge x-ray absorption spectroscopic studies: metal-ligand covalency in a series of transition metal tetrachlorides journal March 1995
X-ray absorption edge spectroscopy of ligands bound to open-shell metal ions: chlorine K-edge studies of covalency in tetrachlorocuprate(2-) journal February 1990
Photoelectron spectra and bonding in cerocene, bis(.pi.-[8]annulene)cerium(IV) journal December 1985
Bis(cyclooctatetraenyl)uranium (uranocene). A new class of sandwich complexes that utilize atomic f orbitals journal December 1968
Di-.pi.-cyclooctatetraenethorium journal December 1969
Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl 6 2– (M = Ti, Zr, Hf, U) and UOCl 5 – Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory journal March 2012
Expanding Rare-Earth Oxidation State Chemistry to Molecular Complexes of Holmium(II) and Erbium(II) journal May 2012
On the Origins of Faster Oxo Exchange for Uranyl(V) versus Plutonyl(V) journal September 2012
Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr 2+ , Gd 2+ , Tb 2+ , and Lu 2+ journal May 2013
Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency
  • Pollock, Christopher J.; Delgado-Jaime, Mario Ulises; Atanasov, Mihail
  • Journal of the American Chemical Society, Vol. 136, Issue 26 https://doi.org/10.1021/ja504182n
journal June 2014
Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl 6 x – ( x = 3, 2) journal February 2015
Structural, Spectroscopic, and Theoretical Comparison of Traditional vs Recently Discovered Ln 2+ Ions in the [K(2.2.2-cryptand)][(C 5 H 4 SiMe 3 ) 3 Ln] Complexes: The Variable Nature of Dy 2+ and Nd 2+ journal December 2014
Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation journal May 2009
The Oxidation State of Ce in the Sandwich Molecule Cerocene journal January 1996
Synthesis and Characterization of the First Sandwich Complex of Trivalent Thorium:  A Structural Comparison with the Uranium Analogue journal July 1999
UCN@ C s (6)-C 82 : An Encapsulated Triangular UCN Cluster with Ambiguous U Oxidation State [U(III) versus U(I)] journal September 2021
Cerium(IV) Imido Complexes: Structural, Computational, and Reactivity Studies journal February 2017
On the Origin of Covalent Bonding in Heavy Actinides journal July 2017
Covalency in Americium(III) Hexachloride journal June 2017
Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO 2 , PrO 2 , and TbO 2 journal November 2017
Energy-Degeneracy-Driven Covalency in Actinide Bonding journal December 2018
Multiple Bonding in Lanthanides and Actinides: Direct Comparison of Covalency in Thorium(IV)- and Cerium(IV)-Imido Complexes journal May 2019
Diuranium(IV) Carbide Cluster U 2 C 2 Stabilized Inside Fullerene Cages journal December 2019
Theoretical Studies of the Properties and Solution Chemistry of AnO 2 2+ and AnO 2 + Aquo Complexes for An = U, Np, and Pu journal July 2000
Electronic Structure and Spectra of Actinyl Ions journal April 2001
Density Functional Studies of Actinyl Aquo Complexes Studied Using Small-Core Effective Core Potentials and a Scalar Four-Component Relativistic Method journal December 2005
Excited States of Large Open-Shell Molecules: An Efficient, General, and Spin-Adapted Approach Based on a Restricted Open-Shell Ground State Wave function journal March 2013
Nature of the Chemical Bond of Aqueous Fe 2+ Probed by Soft X-ray Spectroscopies and ab Initio Calculations journal October 2013
Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study journal January 2014
Combined Experimental and Ab Initio Multireference Configuration Interaction Study of the Resonant Inelastic X-ray Scattering Spectrum of CO 2 journal August 2014
Is Cerocene Really a Ce(III) Compound? All-Electron Spin−Orbit Coupled CASPT2 Calculations on M(η 8 -C 8 H 8 ) 2 (M = Th, Pa, Ce) journal March 2009
Are the Ground States of the Later Actinocenes Multiconfigurational? All-Electron Spin−Orbit Coupled CASPT2 Calculations on An(η 8 -C 8 H 8 ) 2 (An = Th, U, Pu, Cm) journal July 2009
Ab Initio Calculations of X-ray Spectra: Atomic Multiplet and Molecular Orbital Effects in a Multiconfigurational SCF Approach to the L-Edge Spectra of Transition Metal Complexes journal November 2012
Dissecting Local Atomic and Intermolecular Interactions of Transition-Metal Ions in Solution with Selective X-ray Spectroscopy journal November 2012
Synthesis and Properties of Di-π-[8]annulenecerium(IV), Cerocene journal September 2004
Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce 2 (C 8 H 8 ) 3 and Ce(C 8 H 8 ) 2 journal February 2009
The role of the 5f valence orbitals of early actinides in chemical bonding journal July 2017
A diuranium carbide cluster stabilized inside a C80 fullerene cage journal July 2018
Double-slit photoelectron interference in strong-field ionization of the neon dimer journal January 2019
δ and φ back-donation in AnIV metallacycles journal March 2020
Clarifying the quantum mechanical origin of the covalent chemical bond journal September 2020
Isolation and characterization of a covalent CeIV-Aryl complex with an anomalous 13C chemical shift journal March 2021
Metallacyclic actinide catalysts for dinitrogen conversion to ammonia and secondary amines journal May 2020
Extreme multi-valence states in mixed actinide oxides journal May 2019
Conversion of triphenylphosphine oxide to organophosphorus via selective cleavage of C-P, O-P, and C-H bonds with sodium journal January 2020
High-throughput computational X-ray absorption spectroscopy journal July 2018
New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory journal January 2014
Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal–ligand interactions journal January 2015
Covalency hinders AnO 2 (H 2 O) + → AnO(OH) 2 + isomerisation (An = Pa–Pu) journal January 2016
4-Component relativistic calculations of L 3 ionization and excitations for the isoelectronic species UO 2 2+ , OUN + and UN 2 journal January 2016
Quantification of f-element covalency through analysis of the electron density: insights from simulation journal January 2017
The difficult search for organocerium( iv ) compounds journal January 2017
Pentavalent lanthanide nitride-oxides: NPrO and NPrO − complexes with NPr triple bonds journal January 2017
Exploring the electronic structure and speciation of aqueous and colloidal Pu with high energy resolution XANES and computations journal January 2018
Scrutinizing metal–ligand covalency and redox non-innocence via nitrogen K-edge X-ray absorption spectroscopy journal January 2019
Understanding the size effects on the electronic structure of ThO 2 nanoparticles journal January 2019
A computational investigation of orbital overlap versus energy degeneracy covalency in [UE 2 ] 2+ (E = O, S, Se, Te) complexes journal January 2020
Transforming lanthanide and actinide chemistry with nanoparticles journal January 2020
The duality of electron localization and covalency in lanthanide and actinide metallocenes journal January 2020
The missing pieces of the PuO 2 nanoparticle puzzle journal January 2020
Insight into the structure–property relationship of UO 2 nanoparticles journal January 2021
Cerium( iv ) complexes with guanidinate ligands: intense colors and anomalous electronic structures journal January 2021
Enhanced 5f-δ bonding in [U(C 7 H 7 ) 2 ] − : C K-edge XAS, magnetism, and ab initio calculations journal January 2021
An investigation of the electronic structure of bis(η-cyclo-octatetraene)-actinoids by helium-( I ) and -( II ) photoelectron spetroscopy journal January 1977
Parameter-free calculations of X-ray spectra with FEFF9 journal January 2010
Investigating the electronic structure and bonding in uranyl compounds by combining NEXAFS spectroscopy and quantum chemistry journal January 2010
First principles calculations of the structure and V L-edge X-ray absorption spectra of V2O5 using local pair natural orbital coupled cluster theory and spin–orbit coupled configuration interaction approaches journal January 2013
On structure and bonding of lanthanoid trifluorides LnF3 (Ln = La to Lu) journal January 2013
Oxidation state and covalency in f-element metallocenes (M = Ce, Th, Pu): a combined CASSCF and topological study journal January 2013
Introduction of n -electron valence states for multireference perturbation theory journal June 2001
Covalency in the uranyl ion: A polarized x-ray spectroscopic study journal November 2002
Natural transition orbitals journal March 2003
The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems journal May 2008
Determinant based configuration interaction algorithms for complete and restricted configuration interaction spaces journal August 1988
Ground state calculations of di‐π‐cyclooctatetraene cerium journal February 1991
Core and valence excitations in resonant X-ray spectroscopy using restricted excitation window time-dependent density functional theory journal November 2012
A combined DFT and restricted open-shell configuration interaction method including spin-orbit coupling: Application to transition metal L-edge X-ray absorption spectroscopy journal May 2013
New tools for the systematic analysis and visualization of electronic excitations. I. Formalism journal July 2014
Restricted active space calculations of L-edge X-ray absorption spectra: From molecular orbitals to multiplet states journal September 2014
Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling journal August 2015
Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework journal November 2015
Towards an ab initio theory for metal L-edge soft X-ray spectroscopy of molecular aggregates journal August 2016
Comparison of multireference ab initio wavefunction methodologies for X-ray absorption edges: A case study on [Fe(II/III)Cl 4 ] 2–/1– molecules journal March 2019
Coupled cluster study of the x-ray absorption spectra of formaldehyde derivatives at the oxygen, carbon, and fluorine K-edges journal August 2019
Modern quantum chemistry with [Open]Molcas journal June 2020
Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics journal June 2012
The binatural orbitals of electronic transitions journal June 2012
Bonding and bending in the actinyls journal February 1999
Orbitals for Analyzing Bonding and Magnetism of Heavy-Metal Complexes journal September 2015
Pressure-induced changes in L III x-ray-absorption near-edge structure of Ce O 2 and Ce F 4 : Relevance to 4 f -electronic structure journal November 1988
Crystal-structure effects in the Ce L 3 -edge x-ray-absorption spectrum of CeO 2 : Multiple-scattering resonances and many-body final states journal August 1994
State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-Ray Absorption Spectroscopy and Ab Initio Calculations journal August 2013
Mixed valency versus covalency in rare-earth core-electron spectroscopy journal February 1987
Self-Contained Kondo Effect in Single Molecules journal December 2005
Application of FEFF analyses to actinide 5f systems journal May 2020
Spectator and participator processes in the resonant photon-in and photon-out spectra at the Ce L3 edge of CeO2 journal July 2012
CORE-HOLE EFFECT IN THE Ce L 3 X-RAY ABSORPTION SPECTRA OF CeO 2 AND CeFe 2 : NEW EXAMINATION BY USING RESONANT X-RAY EMISSION SPECTROSCOPY journal June 2013
The Basics of Covalent Bonding in Terms of Energy and Dynamics journal June 2020

Similar Records

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?
Journal Article · 2021 · Inorganic Chemistry · OSTI ID:2479712
+1 more
Ab Initio Analysis of Metal–Ligand Bonding in An(COT) 2 with An=Th, U in Their Ground‐ and Core‐Excited States
Journal Article · 2020 · Chemistry - A European Journal · OSTI ID:1582477
Ab Initio Study of Covalency in the Ground versus Core-Excited States and X-ray Absorption Spectra of Actinide Complexes
Journal Article · 2018 · Journal of Physical Chemistry Letters · OSTI ID:2479697

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry