Covalency in actinide( iv ) hexachlorides in relation to the chlorine K-edge X-ray absorption structure

Sergentu, Dumitru-Claudiu; Autschbach, Jochen

doi:10.1039/D1SC06454A

Title: Covalency in actinide( iv ) hexachlorides in relation to the chlorine K-edge X-ray absorption structure

Journal Article · Wed Mar 16 00:00:00 EDT 2022 · Chemical Science

DOI:https://doi.org/10.1039/D1SC06454A· OSTI ID:1846312

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Department of Chemistry, University at Buffalo State University of New York, Buffalo, NY 14260-3000, USA

Chlorine K-edge X-ray absorption near edge structure (XANES) in actinideIV hexachlorides, [AnCl₆]^2- (An = Th–Pu), is calculated with relativistic multiconfiguration wavefunction theory (WFT). Of particular focus is a 3-peak feature emerging from U toward Pu, and its assignment in terms of donation bonding to the An 5f vs. 6d shells. With or without spin–orbit coupling, the calculated and previously measured XANES spectra are in excellent agreement with respect to relative peak positions, relative peak intensities, and peak assignments. Metal–ligand bonding analyses from WFT and Kohn–Sham theory (KST) predict comparable An 5f and 6d covalency from U to Np and Pu. Although some frontier molecular orbitals in the KST calculations display increasing An 5f–Cl 3p mixing from Th to Pu, because of energetic stabilization of 5f relative to the Cl 3p combinations of the matching symmetry, increasing hybridization is neither seen in the WFT natural orbitals, nor is it reflected in the calculated bond orders. The appearance of the pre-edge peaks from U to Pu and their relative intensities are rationalized simply by the energetic separation of transitions to 6d t_2g versus transitions to weakly-bonded and strongly stabilized a_2u, t_2u and t_1u orbitals with 5f character. The study highlights potential pitfalls when interpreting XANES spectra based on ground state Kohn–Sham molecular orbitals.

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Research Organization:: State Univ. of New York (SUNY), Albany, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001136

OSTI ID:: 1846312

Alternate ID(s):: OSTI ID: 1904556

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 13 Journal Issue: 11; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

References (132)

Why Bond Critical Points Are Not “Bond” Critical Points Shahbazian, Shant Chemistry - A European Journal, Vol. 24, Issue 21 https://doi.org/10.1002/chem.201705163	journal	February 2018
Magnetic properties of a fourfold degenerate state: Np4+ ion diluted in Cs2ZrCl6 crystal Hernández, Dayán Páez; Bolvin, Hélène Journal of Electron Spectroscopy and Related Phenomena, Vol. 194 https://doi.org/10.1016/j.elspec.2014.03.002	journal	June 2014
Covalency in AnCp4 (An = Th–Cm): a comparison of molecular orbital, natural population and atoms-in-molecules analyses Tassell, Matthew J.; Kaltsoyannis, Nikolas Dalton Transactions, Vol. 39, Issue 29 https://doi.org/10.1039/c000704h	journal	January 2010
Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal–ligand interactions Tomson, Neil C.; Williams, Kamille D.; Dai, Xuliang Chemical Science, Vol. 6, Issue 4 https://doi.org/10.1039/C4SC03294B	journal	January 2015
A quantum theory of molecular structure and its applications Bader, Richard F. W. Chemical Reviews, Vol. 91, Issue 5 https://doi.org/10.1021/cr00005a013	journal	July 1991
On bond-critical points in QTAIM and weak interactions Wick, Christian R.; Clark, Timothy Journal of Molecular Modeling, Vol. 24, Issue 6 https://doi.org/10.1007/s00894-018-3684-x	journal	May 2018
Transforming lanthanide and actinide chemistry with nanoparticles Pallares, Roger M.; Abergel, Rebecca J. Nanoscale, Vol. 12, Issue 3 https://doi.org/10.1039/C9NR09175K	journal	January 2020
Modern quantum chemistry with [Open]Molcas Aquilante, Francesco; Autschbach, Jochen; Baiardi, Alberto The Journal of Chemical Physics, Vol. 152, Issue 21 https://doi.org/10.1063/5.0004835	journal	June 2020
Enhancing Actinide(III) over Lanthanide(III) Selectivity through Hard-by-Soft Donor Substitution: Exploitation and Implication of Near-Degeneracy-Driven Covalency Sadhu, Biswajit; Dolg, Michael Inorganic Chemistry, Vol. 58, Issue 15 https://doi.org/10.1021/acs.inorgchem.9b00705	journal	July 2019
Beyond structural motifs: the frontier of actinide-containing metal–organic frameworks Martin, Corey R.; Leith, Gabrielle A.; Shustova, Natalia B. Chemical Science, Vol. 12, Issue 21 https://doi.org/10.1039/D1SC01827B	journal	January 2021
Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO ₂ , PrO ₂ , and TbO ₂ Minasian, Stefan G.; Batista, Enrique R.; Booth, Corwin H. Journal of the American Chemical Society, Vol. 139, Issue 49 https://doi.org/10.1021/jacs.7b10361	journal	November 2017
Does covalency really increase across the 5f series? A comparison of molecular orbital, natural population, spin and electron density analyses of AnCp ₃ (An = Th–Cm; Cp = η ⁵ -C ₅ H ₅ ) Kirker, Ian; Kaltsoyannis, Nikolas Dalton Trans., Vol. 40, Issue 1 https://doi.org/10.1039/C0DT01018A	journal	January 2011
Indication of single-crystal PuO $_{2}$ oxidation from O 1 $s$ x-ray absorption spectra Modin, A.; Yun, Y.; Suzuki, M. -T. Physical Review B, Vol. 83, Issue 7 https://doi.org/10.1103/PhysRevB.83.075113	journal	February 2011
Covalency in f-element complexes Neidig, Michael L.; Clark, David L.; Martin, Richard L. Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.04.029	journal	January 2013
Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce ₂ (C ₈ H ₈ ) ₃ and Ce(C ₈ H ₈ ) ₂ Walter, Marc D.; Booth, Corwin H.; Lukens, Wayne W. Organometallics, Vol. 28, Issue 3 https://doi.org/10.1021/om7012327	journal	February 2009
Parameter-free calculations of X-ray spectra with FEFF9 Rehr, John J.; Kas, Joshua J.; Vila, Fernando D. Physical Chemistry Chemical Physics, Vol. 12, Issue 21 https://doi.org/10.1039/b926434e	journal	January 2010
Quantification of f-element covalency through analysis of the electron density: insights from simulation Kerridge, A. Chemical Communications, Vol. 53, Issue 50 https://doi.org/10.1039/C7CC00962C	journal	January 2017
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning Kaltsoyannis, Nikolas Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic3006025	journal	June 2012
Applicability of the no-pair equation with free-particle projection operators to atomic and molecular structure calculations Hess, Bernd A. Physical Review A, Vol. 32, Issue 2 https://doi.org/10.1103/PhysRevA.32.756	journal	August 1985
Self-Contained Kondo Effect in Single Molecules Booth, C. H.; Walter, M. D.; Daniel, M. Physical Review Letters, Vol. 95, Issue 26 https://doi.org/10.1103/PhysRevLett.95.267202	journal	December 2005
A mean-field spin-orbit method applicable to correlated wavefunctions Heß, Bernd A.; Marian, Christel M.; Wahlgren, Ulf Chemical Physics Letters, Vol. 251, Issue 5-6 https://doi.org/10.1016/0009-2614(96)00119-4	journal	March 1996
Covalency in the uranyl ion: A polarized x-ray spectroscopic study Denning, R. G.; Green, J. C.; Hutchings, T. E. The Journal of Chemical Physics, Vol. 117, Issue 17 https://doi.org/10.1063/1.1510445	journal	November 2002
Dissecting Local Atomic and Intermolecular Interactions of Transition-Metal Ions in Solution with Selective X-ray Spectroscopy Wernet, Philippe; Kunnus, Kristjan; Schreck, Simon The Journal of Physical Chemistry Letters, Vol. 3, Issue 23 https://doi.org/10.1021/jz301486u	journal	November 2012
Core and valence excitations in resonant X-ray spectroscopy using restricted excitation window time-dependent density functional theory Zhang, Yu; Biggs, Jason D.; Healion, Daniel The Journal of Chemical Physics, Vol. 137, Issue 19 https://doi.org/10.1063/1.4766356	journal	November 2012
Unraveling the Electronic Structure of Photocatalytic Manganese Complexes by L-Edge X-ray Spectroscopy Bokarev, Sergey I.; Khan, Munirah; Abdel-Latif, Mahmoud K. The Journal of Physical Chemistry C, Vol. 119, Issue 33 https://doi.org/10.1021/acs.jpcc.5b05169	journal	August 2015
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 Sadhu, Biswajit; Dolg, Michael; Kulkarni, Mukund S. Journal of Computational Chemistry, Vol. 41, Issue 15 https://doi.org/10.1002/jcc.26186	journal	March 2020
Development of Single‐Molecule Magnets ^† Shao, Dong; Wang, Xin‐Yi Chinese Journal of Chemistry, Vol. 38, Issue 9 https://doi.org/10.1002/cjoc.202000090	journal	June 2020
A new method of directly determining the core–hole effect in the Ce L3 XAS of mixed valence Ce compounds—An application of resonant X-ray emission spectroscopy Kotani, A.; Kvashnina, K. O.; Butorin, S. M. Journal of Electron Spectroscopy and Related Phenomena, Vol. 184, Issue 3-6 https://doi.org/10.1016/j.elspec.2010.12.028	journal	April 2011
Investigating the electronic structure and bonding in uranyl compounds by combining NEXAFS spectroscopy and quantum chemistry Fillaux, Clara; Guillaumont, Dominique; Berthet, Jean-Claude Physical Chemistry Chemical Physics, Vol. 12, Issue 42 https://doi.org/10.1039/c0cp00386g	journal	January 2010
Multiconfiguration perturbation theory with imaginary level shift Forsberg, Niclas; Malmqvist, Per-Åke Chemical Physics Letters, Vol. 274, Issue 1-3 https://doi.org/10.1016/S0009-2614(97)00669-6	journal	August 1997
f-Orbital covalency in the actinocenes (An = Th–Cm): multiconfigurational studies and topological analysis Kerridge, Andrew RSC Adv., Vol. 4, Issue 24 https://doi.org/10.1039/C3RA47088A	journal	January 2014
New relativistic ANO basis sets for actinide atoms Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke Chemical Physics Letters, Vol. 409, Issue 4-6 https://doi.org/10.1016/j.cplett.2005.05.011	journal	June 2005
Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients Shiozaki, Toru; Győrffy, Werner; Celani, Paolo The Journal of Chemical Physics, Vol. 135, Issue 8 https://doi.org/10.1063/1.3633329	journal	August 2011
Comparison of multireference *ab initio* wavefunction methodologies for X-ray absorption edges: A case study on [Fe(II/III)Cl ₄ ] ^2–/1– molecules Maganas, Dimitrios; Kowalska, Joanna K.; Nooijen, Marcel The Journal of Chemical Physics, Vol. 150, Issue 10 https://doi.org/10.1063/1.5051613	journal	March 2019
Comprehensive Bonding Analysis of Tetravalent f-Element Complexes of the Type [M(salen) ₂ ] Kloditz, Roger; Radoske, Thomas; Schmidt, Moritz Inorganic Chemistry, Vol. 60, Issue 4 https://doi.org/10.1021/acs.inorgchem.0c03424	journal	February 2021
Application of FEFF analyses to actinide 5f systems Tobin, J. G.; Sokaras, D. Journal of Vacuum Science & Technology A, Vol. 38, Issue 3 https://doi.org/10.1116/6.0000215	journal	May 2020
The restricted active space (RAS) state interaction approach with spin–orbit coupling Malmqvist, Per Åke; Roos, Björn O.; Schimmelpfennig, Bernd Chemical Physics Letters, Vol. 357, Issue 3-4 https://doi.org/10.1016/S0009-2614(02)00498-0	journal	May 2002
Understanding the size effects on the electronic structure of ThO ₂ nanoparticles Amidani, Lucia; Plakhova, Tatiana V.; Romanchuk, Anna Yu. Physical Chemistry Chemical Physics, Vol. 21, Issue 20 https://doi.org/10.1039/C9CP01283D	journal	January 2019
The Oxidation State of Ce in the Sandwich Molecule Cerocene Edelstein, N. M.; Allen, P. G.; Bucher, J. J. Journal of the American Chemical Society, Vol. 118, Issue 51 https://doi.org/10.1021/ja962915c	journal	January 1996
Nature of the Chemical Bond of Aqueous Fe 2+ Probed by Soft X-ray Spectroscopies and ab Initio Calculations Atak, Kaan; Bokarev, Sergey I.; Gotz, Malte The Journal of Physical Chemistry B, Vol. 117, Issue 41 https://doi.org/10.1021/jp408212u	journal	October 2013
Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA) ₂ MCl ₆ (M = U, Np, Pt, Sn, Hf, Zr): Phase Transitions in Tetramethylammonium Hexachlorometalate Compounds (TMA) ₂ MCl ₆ (M = U, Np, Pt, Sn, Hf, Zr) Autillo, Matthieu; Wilson, Richard E. European Journal of Inorganic Chemistry, Vol. 2017, Issue 41 https://doi.org/10.1002/ejic.201700764	journal	November 2017
High-throughput computational X-ray absorption spectroscopy Mathew, Kiran; Zheng, Chen; Winston, Donald Scientific Data, Vol. 5, Issue 1 https://doi.org/10.1038/sdata.2018.151	journal	July 2018
4-Component relativistic calculations of L ₃ ionization and excitations for the isoelectronic species UO ₂ ²⁺ , OUN ⁺ and UN ₂ South, Christopher; Shee, Avijit; Mukherjee, Debashis Physical Chemistry Chemical Physics, Vol. 18, Issue 31 https://doi.org/10.1039/C6CP00262E	journal	January 2016
A study of molybdenum behaviour in UO2 by X-ray absorption spectroscopy Martin, Philippe; Ripert, Michel; Carlot, Gaëlle Journal of Nuclear Materials, Vol. 326, Issue 2-3 https://doi.org/10.1016/j.jnucmat.2004.01.006	journal	March 2004
The generalized Douglas–Kroll transformation Wolf, Alexander; Reiher, Markus; Hess, Bernd Artur The Journal of Chemical Physics, Vol. 117, Issue 20 https://doi.org/10.1063/1.1515314	journal	November 2002
Photoelectron spectroscopy and theoretical studies of gaseous uranium hexachlorides in different oxidation states: UCl6q− (q = 0–2) Su, Jing; Dau, Phuong D.; Liu, Hong-Tao The Journal of Chemical Physics, Vol. 142, Issue 13 https://doi.org/10.1063/1.4916399	journal	April 2015
Restricted active space calculations of L-edge X-ray absorption spectra: From molecular orbitals to multiplet states Pinjari, Rahul V.; Delcey, Mickaël G.; Guo, Meiyuan The Journal of Chemical Physics, Vol. 141, Issue 12 https://doi.org/10.1063/1.4896373	journal	September 2014
Towards an ab initio theory for metal L-edge soft X-ray spectroscopy of molecular aggregates Preuße, Marie; Bokarev, Sergey I.; Aziz, Saadullah G. Structural Dynamics, Vol. 3, Issue 6 https://doi.org/10.1063/1.4961953	journal	August 2016
Impact of the Kohn–Sham Delocalization Error on the 4f Shell Localization and Population in Lanthanide Complexes Duignan, Thomas J.; Autschbach, Jochen Journal of Chemical Theory and Computation, Vol. 12, Issue 7 https://doi.org/10.1021/acs.jctc.6b00238	journal	June 2016
Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8 Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K. Journal of Computational Chemistry, Vol. 37, Issue 5 https://doi.org/10.1002/jcc.24221	journal	November 2015
Relativistic electronic-structure calculations employing a two-component no-pair formalism with external-field projection operators Hess, Bernd A. Physical Review A, Vol. 33, Issue 6 https://doi.org/10.1103/PhysRevA.33.3742	journal	June 1986
Relativistic regular two‐component Hamiltonians Lenthe, E. van; Baerends, E. J.; Snijders, J. G. The Journal of Chemical Physics, Vol. 99, Issue 6 https://doi.org/10.1063/1.466059	journal	September 1993
Lanthanide Single-Molecule Magnets Woodruff, Daniel N.; Winpenny, Richard E. P.; Layfield, Richard A. Chemical Reviews, Vol. 113, Issue 7 https://doi.org/10.1021/cr400018q	journal	March 2013
The Application of HEXS and HERFD XANES for Accurate Structural Characterisation of Actinide Nanomaterials: The Case of ThO ₂ Amidani, Lucia; Vaughan, Gavin B. M.; Plakhova, Tatiana V. Chemistry – A European Journal, Vol. 27, Issue 1 https://doi.org/10.1002/chem.202003360	journal	November 2020
Nuclear Magnetic Resonance Measurements and Electronic Structure of Pu(IV) in [(Me) ₄ N] ₂ PuCl ₆ Mounce, Andrew M.; Yasuoka, Hiroshi; Koutroulakis, Georgios Inorganic Chemistry, Vol. 55, Issue 17 https://doi.org/10.1021/acs.inorgchem.6b00735	journal	August 2016
Enhanced 5f-δ bonding in [U(C ₇ H ₇ ) ₂ ] ⁻ : C K-edge XAS, magnetism, and ab initio calculations Qiao, Yusen; Ganguly, Gaurab; Booth, Corwin H. Chemical Communications, Vol. 57, Issue 75 https://doi.org/10.1039/D1CC03414F	journal	January 2021
A Novel Metastable Pentavalent Plutonium Solid Phase on the Pathway from Aqueous Plutonium(VI) to PuO ₂ Nanoparticles Kvashnina, Kristina O.; Romanchuk, Anna Yu.; Pidchenko, Ivan Angewandte Chemie International Edition, Vol. 58, Issue 49 https://doi.org/10.1002/anie.201911637	journal	December 2019
Exploring the electronic structure and speciation of aqueous and colloidal Pu with high energy resolution XANES and computations Vitova, Tonya; Pidchenko, Ivan; Fellhauer, David Chemical Communications, Vol. 54, Issue 91 https://doi.org/10.1039/C8CC06889E	journal	January 2018
Spectator and participator processes in the resonant photon-in and photon-out spectra at the Ce L3 edge of CeO2 Kotani, A.; Kvashnina, K. O.; Butorin, S. M. The European Physical Journal B, Vol. 85, Issue 8 https://doi.org/10.1140/epjb/e2012-30079-1	journal	July 2012
Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study Beekmeyer, Reece; Kerridge, Andrew Inorganics, Vol. 3, Issue 4 https://doi.org/10.3390/inorganics3040482	journal	November 2015
Ab Initio Study of Covalency in the Ground versus Core-Excited States and X-ray Absorption Spectra of Actinide Complexes Sergentu, Dumitru-Claudiu; Duignan, Thomas J.; Autschbach, Jochen The Journal of Physical Chemistry Letters, Vol. 9, Issue 18 https://doi.org/10.1021/acs.jpclett.8b02412	journal	September 2018
Advancement of Actinide Metal–Organic Framework Chemistry via Synthesis of Pu-UiO-66 Hastings, Ashley M.; Ray, Debmalya; Jeong, WooSeok Journal of the American Chemical Society, Vol. 142, Issue 20 https://doi.org/10.1021/jacs.0c01895	journal	April 2020
From Transition Metals to Lanthanides to Actinides: Metal-Mediated Tuning of Electronic Properties of Isostructural Metal–Organic Frameworks Islamoglu, Timur; Ray, Debmalya; Li, Peng Inorganic Chemistry, Vol. 57, Issue 21 https://doi.org/10.1021/acs.inorgchem.8b01748	journal	October 2018
Synthesis and Structure of (Ph ₄ P) ₂ MCl ₆ (M = Ti, Zr, Hf, Th, U, Np, Pu) Minasian, Stefan G.; Boland, Kevin S.; Feller, Russell K. Inorganic Chemistry, Vol. 51, Issue 10 https://doi.org/10.1021/ic300179d	journal	May 2012
Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption Lopata, K.; Van Kuiken, B. E.; Khalil, M. Journal of Chemical Theory and Computation, Vol. 8, Issue 9 https://doi.org/10.1021/ct3005613	journal	August 2012
Differentiating between Trivalent Lanthanides and Actinides Polinski, Matthew J.; Grant, Daniel J.; Wang, Shuao Journal of the American Chemical Society, Vol. 134, Issue 25 https://doi.org/10.1021/ja303804r	journal	June 2012
Endohedral Metallofullerenes: New Structures and Unseen Phenomena Shen, Wangqiang; Hu, Shuaifeng; Lu, Xing Chemistry – A European Journal, Vol. 26, Issue 26 https://doi.org/10.1002/chem.201905306	journal	March 2020
Determinant based configuration interaction algorithms for complete and restricted configuration interaction spaces Olsen, Jeppe; Roos, Björn O.; Jo/rgensen, Poul The Journal of Chemical Physics, Vol. 89, Issue 4 https://doi.org/10.1063/1.455063	journal	August 1988
Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling Grell, Gilbert; Bokarev, Sergey I.; Winter, Bernd The Journal of Chemical Physics, Vol. 143, Issue 7 https://doi.org/10.1063/1.4928511	journal	August 2015
Quantum electrodynamical corrections to the fine structure of helium Douglas, Marvin; Kroll, Norman M. Annals of Physics, Vol. 82, Issue 1 https://doi.org/10.1016/0003-4916(74)90333-9	journal	January 1974
L3 edge X-ray absorption spectrum of CeO2: crystal structure effects Soldatov, A. V.; Ivanchenko, T. S.; Kotani, A. Physica B: Condensed Matter, Vol. 208-209 https://doi.org/10.1016/0921-4526(94)00633-7	journal	March 1995
Introduction of n -electron valence states for multireference perturbation theory Angeli, C.; Cimiraglia, R.; Evangelisti, S. The Journal of Chemical Physics, Vol. 114, Issue 23 https://doi.org/10.1063/1.1361246	journal	June 2001
Polarization Dependent High Energy Resolution X-ray Absorption Study of Dicesium Uranyl Tetrachloride Vitova, Tonya; Green, Jennifer C.; Denning, Robert G. Inorganic Chemistry, Vol. 54, Issue 1 https://doi.org/10.1021/ic5020016	journal	December 2014
Metal and Ligand K-Edge XAS of Organotitanium Complexes: Metal 4p and 3d Contributions to Pre-edge Intensity and Their Contributions to Bonding DeBeer George, Serena; Brant, Patrick; Solomon, Edward I. Journal of the American Chemical Society, Vol. 127, Issue 2 https://doi.org/10.1021/ja044827v	journal	January 2005
Ligand K-Edge X-ray Absorption Spectroscopy: A Direct Probe of Ligand−Metal Covalency Glaser, Thorsten; Hedman, Britt; Hodgson, Keith O. Accounts of Chemical Research, Vol. 33, Issue 12 https://doi.org/10.1021/ar990125c	journal	December 2000
Calculation of X-ray photoelectron spectra with the use of the normalized elimination of the small component method Klooster, Rob; Broer, Ria; Filatov, Michael Chemical Physics, Vol. 395 https://doi.org/10.1016/j.chemphys.2011.05.009	journal	February 2012
Ionic bonding of lanthanides, as influenced by d- and f-atomic orbitals, by core-shells and by relativity Ji, Wen-Xin; Xu, Wei; Schwarz, W. H. Eugen Journal of Computational Chemistry, Vol. 36, Issue 7 https://doi.org/10.1002/jcc.23820	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 Pinjari, Rahul V.; Delcey, Mickaël G.; Guo, Meiyuan Journal of Computational Chemistry, Vol. 37, Issue 5 https://doi.org/10.1002/jcc.24237	journal	October 2015
The duality of electron localization and covalency in lanthanide and actinide metallocenes Smiles, Danil E.; Batista, Enrique R.; Booth, Corwin H. Chemical Science, Vol. 11, Issue 10 https://doi.org/10.1039/C9SC06114B	journal	January 2020
NBO 6.0 : Natural bond orbital analysis program Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank Journal of Computational Chemistry, Vol. 34, Issue 16 https://doi.org/10.1002/jcc.23266	journal	March 2013
A diuranium carbide cluster stabilized inside a C80 fullerene cage Zhang, Xingxing; Li, Wanlu; Feng, Lai Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05210-8	journal	July 2018
Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”? Yu, Xiaojuan; Sergentu, Dumitru-Claudiu; Feng, Rulin Inorganic Chemistry, Vol. 60, Issue 23 https://doi.org/10.1021/acs.inorgchem.1c02374	journal	November 2021
Cerium Tetrakis(tropolonate) and Cerium Tetrakis(acetylacetonate) Are Not Diamagnetic but Temperature-Independent Paramagnets Halbach, Robert L.; Nocton, Grégory; Booth, Corwin H. Inorganic Chemistry, Vol. 57, Issue 12 https://doi.org/10.1021/acs.inorgchem.8b00928	journal	June 2018
Ab Initio Analysis of Metal–Ligand Bonding in An(COT) ₂ with An=Th, U in Their Ground‐ and Core‐Excited States Ganguly, Gaurab; Sergentu, Dumitru‐Claudiu; Autschbach, Jochen Chemistry – A European Journal, Vol. 26, Issue 8 https://doi.org/10.1002/chem.201904166	journal	November 2019
Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl ₆ ^{x –} ( x = 3, 2) Löble, Matthias W.; Keith, Jason M.; Altman, Alison B. Journal of the American Chemical Society, Vol. 137, Issue 7 https://doi.org/10.1021/ja510067v	journal	February 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 Kaindl, G.; Schmiester, G.; Sampathkumaran, E. V. Physical Review B, Vol. 38, Issue 14 https://doi.org/10.1103/PhysRevB.38.10174	journal	November 1988
Simulating Cl K-edge X-ray absorption spectroscopy in MCl6 2− (M = U, Np, Pu) complexes and UOCl5 − using time-dependent density functional theory Govind, Niranjan; de Jong, Wibe A. Theoretical Chemistry Accounts, Vol. 133, Issue 4 https://doi.org/10.1007/s00214-014-1463-z	journal	February 2014
Isolation and Characterization of Light Actinide Metallofullerenes Akiyama, Kazuhiko; Zhao, Yuliang; Sueki, Keisuke Journal of the American Chemical Society, Vol. 123, Issue 1 https://doi.org/10.1021/ja005618n	journal	January 2001
Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An ^IV ( ^Ar acnac) ₄ Complexes (An = Th, U, Np, Pu; ^Ar acnac = Ar N C(Ph)CHC(Ph) O ; Ar = 3,5- ^t Bu ₂ C ₆ H ₃ ) Schnaars, David D.; Gaunt, Andrew J.; Hayton, Trevor W. Inorganic Chemistry, Vol. 51, Issue 15 https://doi.org/10.1021/ic301109f	journal	July 2012
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M. Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1016/0301-0104(80)80045-0	journal	May 1980
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 Kotani, A. Modern Physics Letters B, Vol. 27, Issue 16 https://doi.org/10.1142/S0217984913300123	journal	June 2013
Direct Observation of Molecular Orbital Mixing in a Solvated Organometallic Complex Suljoti, Edlira; Garcia-Diez, Raul; Bokarev, Sergey I. Angewandte Chemie International Edition, Vol. 52, Issue 37 https://doi.org/10.1002/anie.201303310	journal	July 2013
Actinide-based single-molecule magnets Meihaus, Katie R.; Long, Jeffrey R. Dalton Transactions, Vol. 44, Issue 6 https://doi.org/10.1039/C4DT02391A	journal	January 2015
Diuranium(IV) Carbide Cluster U ₂ C ₂ Stabilized Inside Fullerene Cages Zhuang, Jiaxin; Abella, Laura; Sergentu, Dumitru-Claudiu Journal of the American Chemical Society, Vol. 141, Issue 51 https://doi.org/10.1021/jacs.9b10247	journal	December 2019
Multiwfn: A multifunctional wavefunction analyzer Lu, Tian; Chen, Feiwu Journal of Computational Chemistry, Vol. 33, Issue 5 https://doi.org/10.1002/jcc.22885	journal	December 2011
Ligand K-edge x-ray absorption spectroscopic studies: metal-ligand covalency in a series of transition metal tetrachlorides Shadle, Susan E.; Hedman, Britt; Hodgson, Keith O. Journal of the American Chemical Society, Vol. 117, Issue 8 https://doi.org/10.1021/ja00113a015	journal	March 1995
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 Chantzis, Agisilaos; Kowalska, Joanna K.; Maganas, Dimitrios Journal of Chemical Theory and Computation, Vol. 14, Issue 7 https://doi.org/10.1021/acs.jctc.8b00249	journal	May 2018
OpenMolcas: From Source Code to Insight Fdez. Galván, Ignacio; Vacher, Morgane; Alavi, Ali Journal of Chemical Theory and Computation, Vol. 15, Issue 11 https://doi.org/10.1021/acs.jctc.9b00532	journal	September 2019
Many-body effects in core-level spectroscopy of rare-earth compounds Kotani, A.; Jo, T.; Parlebas, J. C. Advances in Physics, Vol. 37, Issue 1 https://doi.org/10.1080/00018738800101359	journal	February 1988
The role of the 5f valence orbitals of early actinides in chemical bonding Vitova, T.; Pidchenko, I.; Fellhauer, D. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms16053	journal	July 2017
Mixed valency versus covalency in rare-earth core-electron spectroscopy Kaindl, G.; Wertheim, G. K.; Schmiester, G. Physical Review Letters, Vol. 58, Issue 6 https://doi.org/10.1103/PhysRevLett.58.606	journal	February 1987
Combined Experimental and Ab Initio Multireference Configuration Interaction Study of the Resonant Inelastic X-ray Scattering Spectrum of CO 2 Maganas, Dimitrios; Kristiansen, Paw; Duda, Laurent-Claudius The Journal of Physical Chemistry C, Vol. 118, Issue 35 https://doi.org/10.1021/jp505628y	journal	August 2014
Two interpretations of the cerocene electronic ground state Mooßen, Oliver; Dolg, Michael Chemical Physics Letters, Vol. 594 https://doi.org/10.1016/j.cplett.2014.01.022	journal	February 2014
State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-Ray Absorption Spectroscopy and Ab Initio Calculations Bokarev, Sergey I.; Dantz, Marcus; Suljoti, Edlira Physical Review Letters, Vol. 111, Issue 8 https://doi.org/10.1103/PhysRevLett.111.083002	journal	August 2013
Investigation of actinide compounds by coupling X-ray absorption spectroscopy and quantum chemistry Fillaux, Clara; Den Auwer, Christophe; Guillaumont, Dominique Journal of Alloys and Compounds, Vol. 444-445 https://doi.org/10.1016/j.jallcom.2007.04.021	journal	October 2007
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
Role of d G/ d w and d V/ d w in AIM Analysis: An Approach to the Nature of Weak to Strong Interactions Nakanishi, Waro; Hayashi, Satoko The Journal of Physical Chemistry A, Vol. 117, Issue 8 https://doi.org/10.1021/jp3095566	journal	February 2013
Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional Ernzerhof, Matthias; Scuseria, Gustavo E. The Journal of Chemical Physics, Vol. 110, Issue 11 https://doi.org/10.1063/1.478401	journal	March 1999
Toward reliable density functional methods without adjustable parameters: The PBE0 model Adamo, Carlo; Barone, Vincenzo The Journal of Chemical Physics, Vol. 110, Issue 13 https://doi.org/10.1063/1.478522	journal	April 1999
New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R. Chem. Sci., Vol. 5, Issue 1 https://doi.org/10.1039/C3SC52030G	journal	January 2014
The missing pieces of the PuO ₂ nanoparticle puzzle Gerber, Evgeny; Romanchuk, Anna Yu.; Pidchenko, Ivan Nanoscale, Vol. 12, Issue 35 https://doi.org/10.1039/D0NR03767B	journal	January 2020
An updated status and trends in actinide metal-organic frameworks (An-MOFs): From synthesis to application Lv, Kai; Fichter, Sebastian; Gu, Mei Coordination Chemistry Reviews, Vol. 446 https://doi.org/10.1016/j.ccr.2021.214011	journal	November 2021
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 Josefsson, Ida; Kunnus, Kristjan; Schreck, Simon The Journal of Physical Chemistry Letters, Vol. 3, Issue 23 https://doi.org/10.1021/jz301479j	journal	November 2012
Optimized Slater-type basis sets for the elements 1-118 Van Lenthe, E.; Baerends, E. J. Journal of Computational Chemistry, Vol. 24, Issue 9 https://doi.org/10.1002/jcc.10255	journal	May 2003
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds Solomon, Edward I.; Hedman, Britt; Hodgson, Keith O. Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.03.020	journal	January 2005
Lanthanide single molecule magnets: progress and perspective Zhang, Peng; Zhang, Li; Tang, Jinkui Dalton Transactions, Vol. 44, Issue 9 https://doi.org/10.1039/C4DT03329A	journal	January 2015
From π Bonds without σ Bonds to the Longest Metal–Metal Bond Ever: A Survey on Actinide–Actinide Bonding in Fullerenes Jaroš, Adam; Foroutan-Nejad, Cina; Straka, Michal Inorganic Chemistry, Vol. 59, Issue 17 https://doi.org/10.1021/acs.inorgchem.0c01713	journal	August 2020
Multicoordinate ligands for actinide/lanthanide separations Dam, Henk H.; Reinhoudt, David N.; Verboom, Willem Chem. Soc. Rev., Vol. 36, Issue 2 https://doi.org/10.1039/B603847F	journal	January 2007
Correlating Electronic Structure and Magnetic Anisotropy in Actinide Complexes [An(COT) ₂ ], An ^III/IV = U, Np, and Pu Singh, Saurabh Kumar; Cramer, Christopher J.; Gagliardi, Laura Inorganic Chemistry, Vol. 59, Issue 10 https://doi.org/10.1021/acs.inorgchem.0c00105	journal	May 2020
Second-order perturbation theory with a CASSCF reference function Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O. The Journal of Physical Chemistry, Vol. 94, Issue 14 https://doi.org/10.1021/j100377a012	journal	July 1990
The restricted active space self-consistent-field method, implemented with a split graph unitary group approach Malmqvist, Per Aake.; Rendell, Alistair.; Roos, Bjoern O. The Journal of Physical Chemistry, Vol. 94, Issue 14 https://doi.org/10.1021/j100377a011	journal	July 1990
Covalency in Americium(III) Hexachloride Cross, Justin N.; Su, Jing; Batista, Enrique R. Journal of the American Chemical Society, Vol. 139, Issue 25 https://doi.org/10.1021/jacs.7b03755	journal	June 2017
The Becke Fuzzy Cells Integration Scheme in the Amsterdam Density Functional Program Suite Franchini, Mirko; Philipsen, Pierre Herman Theodoor; Visscher, Lucas Journal of Computational Chemistry, Vol. 34, Issue 21 https://doi.org/10.1002/jcc.23323	journal	May 2013
Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study Engel, Nicholas; Bokarev, Sergey I.; Suljoti, Edlira The Journal of Physical Chemistry B, Vol. 118, Issue 6 https://doi.org/10.1021/jp411782y	journal	January 2014
Energy-Degeneracy-Driven Covalency in Actinide Bonding Su, Jing; Batista, Enrique R.; Boland, Kevin S. Journal of the American Chemical Society, Vol. 140, Issue 51 https://doi.org/10.1021/jacs.8b09436	journal	December 2018
Electronic Structure and Bonding in Actinyl Ions and their Analogs Denning, Robert G. The Journal of Physical Chemistry A, Vol. 111, Issue 20 https://doi.org/10.1021/jp071061n	journal	May 2007
Recent progress in lanthanide metal–organic frameworks and their derivatives in catalytic applications Zhang, Yue; Liu, Shuo; Zhao, Zi-Song Inorganic Chemistry Frontiers, Vol. 8, Issue 3 https://doi.org/10.1039/D0QI01191F	journal	January 2021
The IPEA dilemma in CASPT2 Zobel, J. Patrick; Nogueira, Juan J.; González, Leticia Chemical Science, Vol. 8, Issue 2 https://doi.org/10.1039/C6SC03759C	journal	January 2017
On structure and bonding of lanthanoid trifluorides LnF3 (Ln = La to Lu) Xu, Wei; Ji, Wen-Xin; Qiu, Yi-Xiang Physical Chemistry Chemical Physics, Vol. 15, Issue 20 https://doi.org/10.1039/c3cp50717c	journal	January 2013
UCN@ C _s (6)-C ₈₂ : An Encapsulated Triangular UCN Cluster with Ambiguous U Oxidation State [U(III) versus U(I)] Meng, Qingyu; Abella, Laura; Yang, Wei Journal of the American Chemical Society, Vol. 143, Issue 39 https://doi.org/10.1021/jacs.1c07519	journal	September 2021
Probing Multiconfigurational States by Spectroscopy: The Cerium XAS L ₃ ‐edge Puzzle Sergentu, Dumitru‐Claudiu; Booth, Corwin H.; Autschbach, Jochen Chemistry – A European Journal, Vol. 27, Issue 25 https://doi.org/10.1002/chem.202100145	journal	March 2021
Direct, atomic orbital, static exchange calculations of photoabsorption spectra of large molecules and clusters Ågren, Hans; Carravetta, Vincenzo; Vahtras, Olav Chemical Physics Letters, Vol. 222, Issue 1-2 https://doi.org/10.1016/0009-2614(94)00318-1	journal	May 1994

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