Magnetic circular dichroism of UCl6– in the ligand-to-metal charge-transfer spectral region

Gendron, Frederic; Fleischauer, Valerie R.; Duignan, Thomas J.; Scott, Brian L.; Löble, Matthias W.; Cary, Samantha K.; Kozimor, Stosh Anthony; Bolvin, Helene; Neidig, Michael L.; Autschbach, Jochen

doi:10.1039/C7CP02572F

Title: Magnetic circular dichroism of UCl₆– in the ligand-to-metal charge-transfer spectral region

Journal Article · Fri Jun 23 04:00:00 UTC 2017 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/C7CP02572F · OSTI ID:1371674

Gendron, Frederic ^[1]; Fleischauer, Valerie R. ^[2]; Duignan, Thomas J. ^[1]; Scott, Brian L. ^[3]; Löble, Matthias W. ^[3]; Cary, Samantha K. ^[3];

^[3]; Bolvin, Helene ^[4]; Neidig, Michael L. ^[5]; Autschbach, Jochen ^[1]

Univ. at Buffalo, NY (United States). Dept. of Chemistry
Univ. of Rochester, NY (United States). Dept. of Chemistry
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of Toulouse (France). Lab. de Physique et de Chimie Quantiques
Univ. of Rochester, NY (United States). Dept. of Chemistry

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl₆- complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E_5/2u and the MCD is a $$C$$-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell, and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the $$C$$-terms: Under O_h double group symmetry, E_5/2u → E_5/2g transitions have negative $$C$$-terms whereas E_5/2u → F_3/2g transitions have positive $$C$$-terms if the ground state g-factor is negative, as it is the case for UCl₆-.

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Research Organization:: Los Alamos National Laboratory (LANL)

Sponsoring Organization:: USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC52-06NA25396; SC0001136; SC0016002

OSTI ID:: 1371674

Report Number(s):: LA-UR-17-23360

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 26 Vol. 19; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (86)

Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal-Field Models Gendron, Frédéric; Páez-Hernández, Dayán; Notter, François-Paul Chemistry - A European Journal, Vol. 20, Issue 26 https://doi.org/10.1002/chem.201305039	journal	May 2014
Structure—Function Correlations in Oxygen Activating Non-heme Iron Enzymes Neidig, Michael L.; Solomon, Edward I. ChemInform, Vol. 37, Issue 11 https://doi.org/10.1002/chin.200611254	journal	March 2006
Magnetic Circular Dichroism of Porphyrin Lanthanide M ³⁺ Complexes : MAGNETIC CIRCULAR DICHROISM OF LANTHANIDE COMPLEXES Andrushchenko, Valery; Padula, Daniele; Zhivotova, Elena Chirality, Vol. 26, Issue 10 https://doi.org/10.1002/chir.22365	journal	August 2014
An Alternative Approach to the g-Matrix: Theory and Applications Bolvin, Hélène ChemPhysChem, Vol. 7, Issue 7 https://doi.org/10.1002/cphc.200600051	journal	June 2006
Molecular Design Guidelines for Large Magnetic Circular Dichroism Intensities in Lanthanide Complexes Kitagawa, Yuichi; Wada, Satoshi; Yanagisawa, Kei ChemPhysChem, Vol. 17, Issue 6 https://doi.org/10.1002/cphc.201501124	journal	January 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
Magnetic circular dichroism of resolved vibronic lines in Cs2ZrCl6:U4+ Piepho, S. B.; Dickinson, J. R.; Schatz, P. N. Physica Status Solidi (b), Vol. 47, Issue 1 https://doi.org/10.1002/pssb.2220470128	journal	September 1971
Electronic structure calculations on workstation computers: The program system turbomole Ahlrichs, Reinhart; Bär, Michael; Häser, Marco Chemical Physics Letters, Vol. 162, Issue 3 https://doi.org/10.1016/0009-2614(89)85118-8	journal	October 1989
Halide complexes of pentavalent uranium Ryan, Jack L. Journal of Inorganic and Nuclear Chemistry, Vol. 33, Issue 1 https://doi.org/10.1016/0022-1902(71)80019-2	journal	January 1971
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
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
Ab initio determinations of magnetic circular dichroism Coriani, Sonia; Jørgensen, Poul; Rizzo, Antonio Chemical Physics Letters, Vol. 300, Issue 1-2 https://doi.org/10.1016/S0009-2614(98)01315-3	journal	January 1999
MCD of uranyl D3h and D5h complexes Görller-Walrand, C.; Colen, W. Inorganica Chimica Acta, Vol. 94, Issue 4 https://doi.org/10.1016/S0020-1693(00)88003-2	journal	April 1984
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
Theoretical insights into the chemical bonding in actinide complexes Dognon, Jean-Pierre Coordination Chemistry Reviews, Vol. 266-267 https://doi.org/10.1016/j.ccr.2013.11.018	journal	May 2014
Electronic Structure and Bonding in Iron(II) and Iron(I) Complexes Bearing Bisphosphine Ligands of Relevance to Iron-Catalyzed C–C Cross-Coupling Kneebone, Jared L.; Fleischauer, Valerie E.; Daifuku, Stephanie L. Inorganic Chemistry, Vol. 55, Issue 1 https://doi.org/10.1021/acs.inorgchem.5b02263	journal	December 2015
Charge-Transfer Versus Charge-Transfer-Like Excitations Revisited Moore, Barry; Sun, Haitao; Govind, Niranjan Journal of Chemical Theory and Computation, Vol. 11, Issue 7 https://doi.org/10.1021/acs.jctc.5b00335	journal	June 2015
Time Dependent Density Functional Theory Study of Magnetic Circular Dichroism Spectra of Gold Clusters Au ₉ (PH ₃ ) ₈ ³⁺ and Au ₉ (PPh ₃ ) ₈ ³⁺ Karimova, Natalia V.; Aikens, Christine M. The Journal of Physical Chemistry A, Vol. 120, Issue 48 https://doi.org/10.1021/acs.jpca.6b10063	journal	November 2016
Giant Faraday Rotation in Mesogenic Organic Molecules Vandendriessche, Stefaan; Van Cleuvenbergen, Stijn; Willot, Pieter Chemistry of Materials, Vol. 25, Issue 7 https://doi.org/10.1021/cm4004118	journal	March 2013
Variational versus Perturbational Treatment of Spin–Orbit Coupling in Relativistic Density Functional Calculations of Electronic g Factors: Effects from Spin-Polarization and Exact Exchange Verma, Prakash; Autschbach, Jochen Journal of Chemical Theory and Computation, Vol. 9, Issue 2 https://doi.org/10.1021/ct3009864	journal	December 2012
Longest-Wavelength Electronic Excitations of Linear Cyanines: The Role of Electron Delocalization and of Approximations in Time-Dependent Density Functional Theory Moore, Barry; Autschbach, Jochen Journal of Chemical Theory and Computation, Vol. 9, Issue 11 https://doi.org/10.1021/ct400649r	journal	September 2013
Electronic Structure of f1 Actinide Complexes. 1. Nonrelativistic and Relativistic Calculations of the Optical Transition Energies of AnX6q- Complexes Kaltsoyannis, Nikolas; Bursten, Bruce E. Inorganic Chemistry, Vol. 34, Issue 10 https://doi.org/10.1021/ic00114a036	journal	May 1995
Theoretical Determination of the Excited States and of g -Factors of the Creutz−Taube Ion, [(NH ₃ ) ₅ −Ru−pyrazine−Ru−(NH ₃ ) ₅ ] ⁵⁺ Bolvin, Hélène Inorganic Chemistry, Vol. 46, Issue 2 https://doi.org/10.1021/ic060816m	journal	January 2007
Electronic spectral studies of some uranium(V) compounds Selbin, Joel; Ortego, James D.; Gritzner, G. Inorganic Chemistry, Vol. 7, Issue 5 https://doi.org/10.1021/ic50063a027	journal	May 1968
Covalency effects on the ligand field splittings of octahedral 5f7 compounds Edelstein, N.; Brown, D.; Whittaker, B. Inorganic Chemistry, Vol. 13, Issue 3 https://doi.org/10.1021/ic50133a013	journal	March 1974
Quasi-relativistic SCF X.alpha. study of octahedral 5f1 complexes Thornton, Geoffrey; Roesch, Notker; Edelstein, Norman Inorganic Chemistry, Vol. 19, Issue 5 https://doi.org/10.1021/ic50207a039	journal	May 1980
Detailed Assignment of the Magnetic Circular Dichroism and UV−vis Spectra of Five-Coordinate High-Spin Ferric [Fe(TPP)(Cl)] Paulat, Florian; Lehnert, Nicolai Inorganic Chemistry, Vol. 47, Issue 11 https://doi.org/10.1021/ic8002838	journal	June 2008
MCD C -Term Signs, Saturation Behavior, and Determination of Band Polarizations in Randomly Oriented Systems with Spin S ≥ ¹ / ₂ . Applications to S = ¹ / ₂ and S = ⁵ / ₂ Neese, Frank; Solomon, Edward I. Inorganic Chemistry, Vol. 38, Issue 8 https://doi.org/10.1021/ic981264d	journal	April 1999
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
Electronic and Spectroscopic Studies of the Non-Heme Reduced Binuclear Iron Sites of Two Ribonucleotide Reductase Variants: Comparison to Reduced Methane Monooxygenase and Contributions to O ₂ Reactivity Wei, Pin-pin; Skulan, Andrew J.; Mitić, Natasa Journal of the American Chemical Society, Vol. 126, Issue 12 https://doi.org/10.1021/ja0374731	journal	March 2004
Spectroscopic and Computational Studies of Co ¹⁺ Cobalamin: Spectral and Electronic Properties of the “Superreduced” B ₁₂ Cofactor Liptak, Mathew D.; Brunold, Thomas C. Journal of the American Chemical Society, Vol. 128, Issue 28 https://doi.org/10.1021/ja061433q	journal	July 2006
Spectroscopic and Electronic Structure Studies of a Dimethyl Sulfoxide Reductase Catalytic Intermediate: Implications for Electron- and Atom-Transfer Reactivity Mtei, Regina P.; Lyashenko, Ganna; Stein, Benjamin Journal of the American Chemical Society, Vol. 133, Issue 25 https://doi.org/10.1021/ja109178q	journal	June 2011
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 Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R. Journal of the American Chemical Society, Vol. 134, Issue 12 https://doi.org/10.1021/ja2105015	journal	March 2012
Outer-Sphere Contributions to the Electronic Structure of Type Zero Copper Proteins Lancaster, Kyle M.; Zaballa, María-Eugenia; Sproules, Stephen Journal of the American Chemical Society, Vol. 134, Issue 19 https://doi.org/10.1021/ja302190r	journal	April 2012
Quantifying the σ and π Interactions between U(V) f Orbitals and Halide, Alkyl, Alkoxide, Amide and Ketimide Ligands Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola Journal of the American Chemical Society, Vol. 135, Issue 29 https://doi.org/10.1021/ja403815h	journal	July 2013
A Combined Mössbauer, Magnetic Circular Dichroism, and Density Functional Theory Approach for Iron Cross-Coupling Catalysis: Electronic Structure, In Situ Formation, and Reactivity of Iron-Mesityl-Bisphosphines Daifuku, Stephanie L.; Al-Afyouni, Malik H.; Snyder, Benjamin E. R. Journal of the American Chemical Society, Vol. 136, Issue 25 https://doi.org/10.1021/ja503596m	journal	June 2014
Detailed Spectroscopic and Theoretical Studies on [Fe(EDTA)(O ₂ )] ³ ^- : Electronic Structure of the Side-on Ferric−Peroxide Bond and Its Relevance to Reactivity Neese, Frank; Solomon, Edward I. Journal of the American Chemical Society, Vol. 120, Issue 49 https://doi.org/10.1021/ja981561h	journal	December 1998
Iron(II) Active Species in Iron–Bisphosphine Catalyzed Kumada and Suzuki–Miyaura Cross-Couplings of Phenyl Nucleophiles and Secondary Alkyl Halides Daifuku, Stephanie L.; Kneebone, Jared L.; Snyder, Benjamin E. R. Journal of the American Chemical Society, Vol. 137, Issue 35 https://doi.org/10.1021/jacs.5b06648	journal	August 2015
Magnetic Circular Dichroism Evidence for an Unusual Electronic Structure of a Tetracarbene–Oxoiron(IV) Complex Ye, Shengfa; Kupper, Claudia; Meyer, Steffen Journal of the American Chemical Society, Vol. 138, Issue 43 https://doi.org/10.1021/jacs.6b07708	journal	October 2016
The A and B Terms of Magnetic Circular Dichroism Revisited Solheim, Harald; Ruud, Kenneth; Coriani, Sonia The Journal of Physical Chemistry A, Vol. 112, Issue 40 https://doi.org/10.1021/jp803135x	journal	October 2008
Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy Formanuik, Alasdair; Ariciu, Ana-Maria; Ortu, Fabrizio Nature Chemistry, Vol. 9, Issue 6 https://doi.org/10.1038/nchem.2692	journal	December 2016
Spectroscopic properties of uranyl chloride complexes in non-aqueous solvents Görller-Walrand, Christiane; De Houwer, Sandy; Fluyt, Linda Phys. Chem. Chem. Phys., Vol. 6, Issue 13 https://doi.org/10.1039/B317002K	journal	January 2004
A combined magnetic circular dichroism and density functional theory approach for the elucidation of electronic structure and bonding in three- and four-coordinate iron( ii )–N-heterocyclic carbene complexes Fillman, Kathlyn L.; Przyojski, Jacob A.; Al-Afyouni, Malik H. Chemical Science, Vol. 6, Issue 2 https://doi.org/10.1039/C4SC02791D	journal	January 2015
Magnetic circular dichroism and computational study of mononuclear and dinuclear iron( iv ) complexes Ye, Shengfa; Xue, Genqiang; Krivokapic, Itana Chemical Science, Vol. 6, Issue 5 https://doi.org/10.1039/C4SC03268C	journal	January 2015
Single-ion 4f element magnetism: an ab-initio look at Ln(COT) ₂ ⁻ Gendron, Frédéric; Pritchard, Benjamin; Bolvin, Hélène Dalton Transactions, Vol. 44, Issue 46 https://doi.org/10.1039/C5DT02858B	journal	January 2015
Magnetic circular dichroism studies of iron( ii ) binding to human calprotectin Baker, Tessa M.; Nakashige, Toshiki G.; Nolan, Elizabeth M. Chemical Science, Vol. 8, Issue 2 https://doi.org/10.1039/C6SC03487J	journal	January 2017
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Structure–function correlations in oxygen activating non-heme iron enzymes Neidig, Michael L.; Solomon, Edward I. Chemical Communications, Issue 47 https://doi.org/10.1039/b510233m	journal	January 2005
Recent advances in computational actinoid chemistry Wang, Dongqi; van Gunsteren, Wilfred F.; Chai, Zhifang Chemical Society Reviews, Vol. 41, Issue 17 https://doi.org/10.1039/c2cs15354h	journal	January 2012
Electronic spectra and magnetic circular dichroism of the uranyl ion. Part II. The effect of reduced symmetry on the spectra Brint, Paul; McCaffery, Anthony J. Journal of the Chemical Society, Dalton Transactions, Issue 1 https://doi.org/10.1039/dt9740000051	journal	January 1974
Magnetic circular dichroism of symmetry and spin forbidden transitions of high-spin metal ions Oganesyan, Vasily S.; Thomson, Andrew J. The Journal of Chemical Physics, Vol. 113, Issue 12 https://doi.org/10.1063/1.1289531	journal	January 2000
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
Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann The Journal of Chemical Physics, Vol. 118, Issue 2 https://doi.org/10.1063/1.1521431	journal	January 2003
Theory of Magnetic Circular Dichroism Stephens, P. J. The Journal of Chemical Physics, Vol. 52, Issue 7 https://doi.org/10.1063/1.1673514	journal	January 1970
Calculation of the A term of magnetic circular dichroism based on time dependent-density functional theory I. Formulation and implementation Seth, Michael; Ziegler, Tom; Banerjee, Arup The Journal of Chemical Physics, Vol. 120, Issue 23 https://doi.org/10.1063/1.1747828	journal	June 2004
Calculated optical and magnetic properties of hexafluorouranate (V) anion: UF[sub 6][sup −] Arratia-Pérez, Ramiro; Hernandez-Acevedo, Lucia; Malli, Gulzari L. The Journal of Chemical Physics, Vol. 121, Issue 16 https://doi.org/10.1063/1.1799891	journal	January 2004
Ab initio calculation of the C∕D ratio of magnetic circular dichroism Seth, Michael; Ziegler, Tom; Autschbach, Jochen The Journal of Chemical Physics, Vol. 122, Issue 9 https://doi.org/10.1063/1.1856453	journal	March 2005
Importance of vibronic effects on the circular dichroism spectrum of dimethyloxirane Neugebauer, Johannes; Jan Baerends, Evert; Nooijen, Marcel The Journal of Chemical Physics, Vol. 122, Issue 23 https://doi.org/10.1063/1.1927519	journal	June 2005
Relativistic molecular orbital study of the optical and magnetic properties of hexachloro protactinate (IV): PaCl62− Arratia-Pérez, Ramiro; Malli, Gulzari L. The Journal of Chemical Physics, Vol. 124, Issue 7 https://doi.org/10.1063/1.2173251	journal	February 2006
Calculation of the magnetic circular dichroism B term from the imaginary part of the Verdet constant using damped time-dependent density functional theory Krykunov, Mykhaylo; Seth, Michael; Ziegler, Tom The Journal of Chemical Physics, Vol. 127, Issue 24 https://doi.org/10.1063/1.2806990	journal	December 2007
First-principles calculations of magnetic circular dichroism spectra Ganyushin, Dmitry; Neese, Frank The Journal of Chemical Physics, Vol. 128, Issue 11 https://doi.org/10.1063/1.2894297	journal	March 2008
Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism: Calculation of B terms Seth, Michael; Krykunov, Mykhaylo; Ziegler, Tom The Journal of Chemical Physics, Vol. 128, Issue 14 https://doi.org/10.1063/1.2901967	journal	April 2008
Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism. II. Calculation of A terms Seth, Michael; Krykunov, Mykhaylo; Ziegler, Tom The Journal of Chemical Physics, Vol. 128, Issue 23 https://doi.org/10.1063/1.2933550	journal	June 2008
Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism. III. Temperature-dependent magnetic circular dichroism induced by spin-orbit coupling Seth, Michael; Ziegler, Tom; Autschbach, Jochen The Journal of Chemical Physics, Vol. 129, Issue 10 https://doi.org/10.1063/1.2976568	journal	September 2008
Optical and magnetic properties of the 5f[sup 1]AnX[sub 6][sup q−] series: A theoretical study Notter, François-Paul; Bolvin, Hélène The Journal of Chemical Physics, Vol. 130, Issue 18 https://doi.org/10.1063/1.3124193	journal	January 2009
Fully optimized contracted Gaussian basis sets for atoms Li to Kr Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 97, Issue 4 https://doi.org/10.1063/1.463096	journal	August 1992
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide Küchle, W.; Dolg, M.; Stoll, H. The Journal of Chemical Physics, Vol. 100, Issue 10 https://doi.org/10.1063/1.466847	journal	May 1994
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
A fully variational spin-orbit coupled complete active space self-consistent field approach: Application to electron paramagnetic resonance g-tensors Ganyushin, Dmitry; Neese, Frank The Journal of Chemical Physics, Vol. 138, Issue 10 https://doi.org/10.1063/1.4793736	journal	March 2013
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
Ab initio all-electron fully relativistic Dirac—Fock self-consistent field calculations for UCI ₆ Malli, Gulzari L. Molecular Physics, Vol. 101, Issue 1-2 https://doi.org/10.1080/00268970210162790	journal	January 2003
The electronic structure of the uranyl ion: Part I. The electronic spectrum of Cs2UO2Cl4 Denning, R. G.; Snellgrove, T. R.; Woodwark, D. R. Molecular Physics, Vol. 32, Issue 2 https://doi.org/10.1080/00268977600103211	journal	August 1976
The electronic structure of the uranyl ion: II. The electronic spectra of CsUO Denning, R. G.; Foster, D. N. P.; Snellgrove, T. R. Molecular Physics, Vol. 37, Issue 4 https://doi.org/10.1080/00268977900100831	journal	April 1979
The electronic structure of actinyl ions: V. Denning, R. G.; Norris, J. O. W.; Brown, D. Molecular Physics, Vol. 46, Issue 2 https://doi.org/10.1080/00268978200101261	journal	June 1982
The electronic structure of actinyl ions: VI. Charge transfer transitions in Cs Denning, R. G.; Norris, J. O. W.; Brown, D. Molecular Physics, Vol. 46, Issue 2 https://doi.org/10.1080/00268978200101271	journal	June 1982
The electronic structure of actinyl ions: VII. The spectrum of Cs ₂ UO ₂ Br _x Cl _{4- x} Denning, R. G.; Norris, J. O. W.; Laing, P. J. Molecular Physics, Vol. 54, Issue 3 https://doi.org/10.1080/00268978500100561	journal	February 1985
The electronic structure of actinyl ions: Part IX. The electronic spectroscopy of (PPh ₄ )UOCl ₅ Bartleet, J. M.; Denning, R. G.; Morrison, I. D. Molecular Physics, Vol. 75, Issue 3 https://doi.org/10.1080/00268979200100431	journal	February 1992
Orbitals for Analyzing Bonding and Magnetism of Heavy-Metal Complexes Autschbach, Jochen Comments on Inorganic Chemistry, Vol. 36, Issue 4 https://doi.org/10.1080/02603594.2015.1121874	journal	September 2015
Unique Definition of the Zeeman-Splitting g Tensor of a Kramers Doublet Chibotaru, L. F.; Ceulemans, A.; Bolvin, H. Physical Review Letters, Vol. 101, Issue 3 https://doi.org/10.1103/PhysRevLett.101.033003	journal	July 2008
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Magnetic Optical Activity Buckingham, A. D.; Stephens, P. J. Annual Review of Physical Chemistry, Vol. 17, Issue 1 https://doi.org/10.1146/annurev.pc.17.100166.002151	journal	October 1966
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
Exatomic: V0.3.0 Marchenko, Alex; Duignan, Tom Zenodo, 1 ZIP file (177.3 kB) https://doi.org/10.5281/zenodo.60053	code	August 2016

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Title: Magnetic circular dichroism of UCl₆– in the ligand-to-metal charge-transfer spectral region