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Title: Magnetic circular dichroism of UCl 6– in the ligand-to-metal charge-transfer spectral region

Abstract

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl 6- 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 UCl 6-.

Authors:
 [1];  [2];  [1];  [3];  [3];  [3]; ORCiD logo [3];  [4];  [5];  [1]
  1. Univ. at Buffalo, NY (United States). Dept. of Chemistry
  2. Univ. of Rochester, NY (United States). Dept. of Chemistry
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Univ. of Toulouse (France). Lab. de Physique et de Chimie Quantiques
  5. Univ. of Rochester, NY (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1371674
Report Number(s):
LA-UR-17-23360
Journal ID: ISSN 1463-9076
Grant/Contract Number:  
AC52-06NA25396; FG02-09ER16066; SC0001136; SC0016002
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 26; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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., and Autschbach, Jochen. Magnetic circular dichroism of UCl6– in the ligand-to-metal charge-transfer spectral region. United States: N. p., 2017. Web. doi:10.1039/C7CP02572F.
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. Magnetic circular dichroism of UCl6– in the ligand-to-metal charge-transfer spectral region. United States. doi:10.1039/C7CP02572F.
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., and Autschbach, Jochen. Fri . "Magnetic circular dichroism of UCl6– in the ligand-to-metal charge-transfer spectral region". United States. doi:10.1039/C7CP02572F. https://www.osti.gov/servlets/purl/1371674.
@article{osti_1371674,
title = {Magnetic circular dichroism of UCl6– in the ligand-to-metal charge-transfer spectral region},
author = {Gendron, Frederic and Fleischauer, Valerie R. and Duignan, Thomas J. and Scott, Brian L. and Löble, Matthias W. and Cary, Samantha K. and Kozimor, Stosh Anthony and Bolvin, Helene and Neidig, Michael L. and Autschbach, Jochen},
abstractNote = {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 E5/2u 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 Oh double group symmetry, E5/2u → E5/2g transitions have negative $C$-terms whereas E5/2u → F3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl6-.},
doi = {10.1039/C7CP02572F},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 26,
volume = 19,
place = {United States},
year = {2017},
month = {6}
}

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Figures / Tables:

Figure 1 Figure 1: Isosurfaces (± 0.03 au) of selected natural orbitals of UCl6-. (a) Ligand based orbitals of gerade symmetry comprising the ras1 space in the LMCT calculations, and (b) 5ƒ orbitals of ungerade symmetry comprising the ras2 space (RAS(19,16)SCF calculation). (c) 6d orbitals of gerade symmetry comprising the ras3 spacemore » (RAS(1,12)SCF calculation).« less

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Works referenced in this record:

Structure–function correlations in oxygen activating non-heme iron enzymes
journal, January 2005

  • Neidig, Michael L.; Solomon, Edward I.
  • Chemical Communications, Issue 47
  • DOI: 10.1039/b510233m

Ab initio all-electron fully relativistic Dirac—Fock self-consistent field calculations for UCI 6
journal, January 2003


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Longest-Wavelength Electronic Excitations of Linear Cyanines: The Role of Electron Delocalization and of Approximations in Time-Dependent Density Functional Theory
journal, September 2013

  • Moore, Barry; Autschbach, Jochen
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 11
  • DOI: 10.1021/ct400649r

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
journal, December 1998

  • Neese, Frank; Solomon, Edward I.
  • Journal of the American Chemical Society, Vol. 120, Issue 49
  • DOI: 10.1021/ja981561h

The electronic structure of actinyl ions: V.
journal, June 1982


Magnetic Optical Activity
journal, October 1966


Covalency effects on the ligand field splittings of octahedral 5f7 compounds
journal, March 1974

  • Edelstein, N.; Brown, D.; Whittaker, B.
  • Inorganic Chemistry, Vol. 13, Issue 3
  • DOI: 10.1021/ic50133a013

Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy
journal, December 2016

  • Formanuik, Alasdair; Ariciu, Ana-Maria; Ortu, Fabrizio
  • Nature Chemistry, Vol. 9, Issue 6
  • DOI: 10.1038/nchem.2692

Magnetic circular dichroism of resolved vibronic lines in Cs2ZrCl6:U4+
journal, September 1971

  • Piepho, S. B.; Dickinson, J. R.; Schatz, P. N.
  • Physica Status Solidi (b), Vol. 47, Issue 1
  • DOI: 10.1002/pssb.2220470128

Electronic spectral studies of some uranium(V) compounds
journal, May 1968

  • Selbin, Joel; Ortego, James D.; Gritzner, G.
  • Inorganic Chemistry, Vol. 7, Issue 5
  • DOI: 10.1021/ic50063a027

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
journal, June 2014

  • Daifuku, Stephanie L.; Al-Afyouni, Malik H.; Snyder, Benjamin E. R.
  • Journal of the American Chemical Society, Vol. 136, Issue 25
  • DOI: 10.1021/ja503596m

Magnetic circular dichroism of symmetry and spin forbidden transitions of high-spin metal ions
journal, January 2000

  • Oganesyan, Vasily S.; Thomson, Andrew J.
  • The Journal of Chemical Physics, Vol. 113, Issue 12
  • DOI: 10.1063/1.1289531

Detailed Assignment of the Magnetic Circular Dichroism and UV−vis Spectra of Five-Coordinate High-Spin Ferric [Fe(TPP)(Cl)]
journal, June 2008

  • Paulat, Florian; Lehnert, Nicolai
  • Inorganic Chemistry, Vol. 47, Issue 11
  • DOI: 10.1021/ic8002838

Molecular Design Guidelines for Large Magnetic Circular Dichroism Intensities in Lanthanide Complexes
journal, January 2016


Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994

  • Küchle, W.; Dolg, M.; Stoll, H.
  • The Journal of Chemical Physics, Vol. 100, Issue 10
  • DOI: 10.1063/1.466847

Recent advances in computational actinoid chemistry
journal, January 2012

  • Wang, Dongqi; van Gunsteren, Wilfred F.; Chai, Zhifang
  • Chemical Society Reviews, Vol. 41, Issue 17
  • DOI: 10.1039/c2cs15354h

Electronic structure calculations on workstation computers: The program system turbomole
journal, October 1989


Quantifying the σ and π Interactions between U(V) f Orbitals and Halide, Alkyl, Alkoxide, Amide and Ketimide Ligands
journal, July 2013

  • Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola
  • Journal of the American Chemical Society, Vol. 135, Issue 29
  • DOI: 10.1021/ja403815h

The electronic structure of actinyl ions: VI. Charge transfer transitions in Cs
journal, June 1982


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

Exatomic: V0.3.0
code, August 2016


Single-ion 4f element magnetism: an ab-initio look at Ln(COT) 2
journal, January 2015

  • Gendron, Frédéric; Pritchard, Benjamin; Bolvin, Hélène
  • Dalton Transactions, Vol. 44, Issue 46
  • DOI: 10.1039/C5DT02858B

Magnetic Circular Dichroism Evidence for an Unusual Electronic Structure of a Tetracarbene–Oxoiron(IV) Complex
journal, October 2016

  • Ye, Shengfa; Kupper, Claudia; Meyer, Steffen
  • Journal of the American Chemical Society, Vol. 138, Issue 43
  • DOI: 10.1021/jacs.6b07708

The A and B Terms of Magnetic Circular Dichroism Revisited
journal, October 2008

  • Solheim, Harald; Ruud, Kenneth; Coriani, Sonia
  • The Journal of Physical Chemistry A, Vol. 112, Issue 40
  • DOI: 10.1021/jp803135x

Fully optimized contracted Gaussian basis sets for atoms Li to Kr
journal, August 1992

  • Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463096

Ab initio determinations of magnetic circular dichroism
journal, January 1999


MCD of uranyl D3h and D5h complexes
journal, April 1984


Calculated optical and magnetic properties of hexafluorouranate (V) anion: UF[sub 6][sup −]
journal, January 2004

  • Arratia-Pérez, Ramiro; Hernandez-Acevedo, Lucia; Malli, Gulzari L.
  • The Journal of Chemical Physics, Vol. 121, Issue 16
  • DOI: 10.1063/1.1799891

Orbitals for Analyzing Bonding and Magnetism of Heavy-Metal Complexes
journal, September 2015


Electronic spectra and magnetic circular dichroism of the uranyl ion. Part II. The effect of reduced symmetry on the spectra
journal, January 1974

  • Brint, Paul; McCaffery, Anthony J.
  • Journal of the Chemical Society, Dalton Transactions, Issue 1
  • DOI: 10.1039/dt9740000051

Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism. II. Calculation of A terms
journal, June 2008

  • Seth, Michael; Krykunov, Mykhaylo; Ziegler, Tom
  • The Journal of Chemical Physics, Vol. 128, Issue 23
  • DOI: 10.1063/1.2933550

Ab initio calculation of the C∕D ratio of magnetic circular dichroism
journal, March 2005

  • Seth, Michael; Ziegler, Tom; Autschbach, Jochen
  • The Journal of Chemical Physics, Vol. 122, Issue 9
  • DOI: 10.1063/1.1856453

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

Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal-Field Models
journal, May 2014

  • Gendron, Frédéric; Páez-Hernández, Dayán; Notter, François-Paul
  • Chemistry - A European Journal, Vol. 20, Issue 26
  • DOI: 10.1002/chem.201305039

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+
journal, November 2016

  • Karimova, Natalia V.; Aikens, Christine M.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 48
  • DOI: 10.1021/acs.jpca.6b10063

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

The electronic structure of the uranyl ion: Part I. The electronic spectrum of Cs2UO2Cl4
journal, August 1976


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


Magnetic circular dichroism and computational study of mononuclear and dinuclear iron( iv ) complexes
journal, January 2015

  • Ye, Shengfa; Xue, Genqiang; Krivokapic, Itana
  • Chemical Science, Vol. 6, Issue 5
  • DOI: 10.1039/C4SC03268C

Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


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


Electronic Structure and Bonding in Iron(II) and Iron(I) Complexes Bearing Bisphosphine Ligands of Relevance to Iron-Catalyzed C–C Cross-Coupling
journal, December 2015


Theoretical insights into the chemical bonding in actinide complexes
journal, May 2014


Relativistic molecular orbital study of the optical and magnetic properties of hexachloro protactinate (IV): PaCl62−
journal, February 2006

  • Arratia-Pérez, Ramiro; Malli, Gulzari L.
  • The Journal of Chemical Physics, Vol. 124, Issue 7
  • DOI: 10.1063/1.2173251

Quasi-relativistic SCF X.alpha. study of octahedral 5f1 complexes
journal, May 1980

  • Thornton, Geoffrey; Roesch, Notker; Edelstein, Norman
  • Inorganic Chemistry, Vol. 19, Issue 5
  • DOI: 10.1021/ic50207a039

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


Importance of vibronic effects on the circular dichroism spectrum of dimethyloxirane
journal, June 2005

  • Neugebauer, Johannes; Jan Baerends, Evert; Nooijen, Marcel
  • The Journal of Chemical Physics, Vol. 122, Issue 23
  • DOI: 10.1063/1.1927519

Calculation of the magnetic circular dichroism B term from the imaginary part of the Verdet constant using damped time-dependent density functional theory
journal, December 2007

  • Krykunov, Mykhaylo; Seth, Michael; Ziegler, Tom
  • The Journal of Chemical Physics, Vol. 127, Issue 24
  • DOI: 10.1063/1.2806990

Charge-Transfer Versus Charge-Transfer-Like Excitations Revisited
journal, June 2015

  • Moore, Barry; Sun, Haitao; Govind, Niranjan
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 7
  • DOI: 10.1021/acs.jctc.5b00335

Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional
journal, March 1999

  • Ernzerhof, Matthias; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 110, Issue 11
  • DOI: 10.1063/1.478401

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

Giant Faraday Rotation in Mesogenic Organic Molecules
journal, March 2013

  • Vandendriessche, Stefaan; Van Cleuvenbergen, Stijn; Willot, Pieter
  • Chemistry of Materials, Vol. 25, Issue 7
  • DOI: 10.1021/cm4004118

Magnetic Circular Dichroism of Porphyrin Lanthanide M 3+ Complexes : MAGNETIC CIRCULAR DICHROISM OF LANTHANIDE COMPLEXES
journal, August 2014

  • Andrushchenko, Valery; Padula, Daniele; Zhivotova, Elena
  • Chirality, Vol. 26, Issue 10
  • DOI: 10.1002/chir.22365

Theory of Magnetic Circular Dichroism
journal, January 1970

  • Stephens, P. J.
  • The Journal of Chemical Physics, Vol. 52, Issue 7
  • DOI: 10.1063/1.1673514

First-principles calculations of magnetic circular dichroism spectra
journal, March 2008

  • Ganyushin, Dmitry; Neese, Frank
  • The Journal of Chemical Physics, Vol. 128, Issue 11
  • DOI: 10.1063/1.2894297

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


Magnetic circular dichroism studies of iron( ii ) binding to human calprotectin
journal, January 2017

  • Baker, Tessa M.; Nakashige, Toshiki G.; Nolan, Elizabeth M.
  • Chemical Science, Vol. 8, Issue 2
  • DOI: 10.1039/C6SC03487J

Calculation of the A term of magnetic circular dichroism based on time dependent-density functional theory I. Formulation and implementation
journal, June 2004

  • Seth, Michael; Ziegler, Tom; Banerjee, Arup
  • The Journal of Chemical Physics, Vol. 120, Issue 23
  • DOI: 10.1063/1.1747828

Spectroscopic and Computational Studies of Co 1+ Cobalamin:  Spectral and Electronic Properties of the “Superreduced” B 12 Cofactor
journal, July 2006

  • Liptak, Mathew D.; Brunold, Thomas C.
  • Journal of the American Chemical Society, Vol. 128, Issue 28
  • DOI: 10.1021/ja061433q

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

Halide complexes of pentavalent uranium
journal, January 1971


The electronic structure of the uranyl ion: II. The electronic spectra of CsUO
journal, April 1979


Second-order perturbation theory with a CASSCF reference function
journal, July 1990

  • Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O.
  • The Journal of Physical Chemistry, Vol. 94, Issue 14
  • DOI: 10.1021/j100377a012

The generalized Douglas–Kroll transformation
journal, November 2002

  • Wolf, Alexander; Reiher, Markus; Hess, Bernd Artur
  • The Journal of Chemical Physics, Vol. 117, Issue 20
  • DOI: 10.1063/1.1515314

Spectroscopic and Electronic Structure Studies of a Dimethyl Sulfoxide Reductase Catalytic Intermediate: Implications for Electron- and Atom-Transfer Reactivity
journal, June 2011

  • Mtei, Regina P.; Lyashenko, Ganna; Stein, Benjamin
  • Journal of the American Chemical Society, Vol. 133, Issue 25
  • DOI: 10.1021/ja109178q

Photoelectron spectroscopy and theoretical studies of gaseous uranium hexachlorides in different oxidation states: UCl6q− (q = 0–2)
journal, April 2015

  • Su, Jing; Dau, Phuong D.; Liu, Hong-Tao
  • The Journal of Chemical Physics, Vol. 142, Issue 13
  • DOI: 10.1063/1.4916399

Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8
journal, November 2015

  • Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K.
  • Journal of Computational Chemistry, Vol. 37, Issue 5
  • DOI: 10.1002/jcc.24221

Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism: Calculation of B terms
journal, April 2008

  • Seth, Michael; Krykunov, Mykhaylo; Ziegler, Tom
  • The Journal of Chemical Physics, Vol. 128, Issue 14
  • DOI: 10.1063/1.2901967

Spectroscopic properties of uranyl chloride complexes in non-aqueous solvents
journal, January 2004

  • Görller-Walrand, Christiane; De Houwer, Sandy; Fluyt, Linda
  • Phys. Chem. Chem. Phys., Vol. 6, Issue 13
  • DOI: 10.1039/B317002K

A fully variational spin-orbit coupled complete active space self-consistent field approach: Application to electron paramagnetic resonance g-tensors
journal, March 2013

  • Ganyushin, Dmitry; Neese, Frank
  • The Journal of Chemical Physics, Vol. 138, Issue 10
  • DOI: 10.1063/1.4793736

Iron(II) Active Species in Iron–Bisphosphine Catalyzed Kumada and Suzuki–Miyaura Cross-Couplings of Phenyl Nucleophiles and Secondary Alkyl Halides
journal, August 2015

  • Daifuku, Stephanie L.; Kneebone, Jared L.; Snyder, Benjamin E. R.
  • Journal of the American Chemical Society, Vol. 137, Issue 35
  • DOI: 10.1021/jacs.5b06648

Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials
journal, January 2003

  • Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann
  • The Journal of Chemical Physics, Vol. 118, Issue 2
  • DOI: 10.1063/1.1521431

Outer-Sphere Contributions to the Electronic Structure of Type Zero Copper Proteins
journal, April 2012

  • Lancaster, Kyle M.; Zaballa, María-Eugenia; Sproules, Stephen
  • Journal of the American Chemical Society, Vol. 134, Issue 19
  • DOI: 10.1021/ja302190r

    Works referencing / citing this record:

    Exatomic: V0.3.0
    code, August 2016


    CCDC 1544486: Experimental Crystal Structure Determination: XIMNEO01 : tetraphenylphosphonium hexachloro-uranium(v)
    dataset, April 2017

    • Gendron, Frédéric; Fleischauer, Valerie E.; Duignan, Thomas J.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc1nv54t

    Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal-Field Models
    journal, May 2014

    • Gendron, Frédéric; Páez-Hernández, Dayán; Notter, François-Paul
    • Chemistry - A European Journal, Vol. 20, Issue 26
    • DOI: 10.1002/chem.201305039

    Magnetic Circular Dichroism of Porphyrin Lanthanide M 3+ Complexes : MAGNETIC CIRCULAR DICHROISM OF LANTHANIDE COMPLEXES
    journal, August 2014

    • Andrushchenko, Valery; Padula, Daniele; Zhivotova, Elena
    • Chirality, Vol. 26, Issue 10
    • DOI: 10.1002/chir.22365

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


    Molecular Design Guidelines for Large Magnetic Circular Dichroism Intensities in Lanthanide Complexes
    journal, January 2016


    Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8
    journal, November 2015

    • Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K.
    • Journal of Computational Chemistry, Vol. 37, Issue 5
    • DOI: 10.1002/jcc.24221

    Magnetic circular dichroism of resolved vibronic lines in Cs2ZrCl6:U4+
    journal, September 1971

    • Piepho, S. B.; Dickinson, J. R.; Schatz, P. N.
    • Physica Status Solidi (b), Vol. 47, Issue 1
    • DOI: 10.1002/pssb.2220470128

    Electronic structure calculations on workstation computers: The program system turbomole
    journal, October 1989


    Halide complexes of pentavalent uranium
    journal, January 1971


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


    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

    Theoretical insights into the chemical bonding in actinide complexes
    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
    journal, December 2015


    Charge-Transfer Versus Charge-Transfer-Like Excitations Revisited
    journal, June 2015

    • Moore, Barry; Sun, Haitao; Govind, Niranjan
    • Journal of Chemical Theory and Computation, Vol. 11, Issue 7
    • DOI: 10.1021/acs.jctc.5b00335

    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+
    journal, November 2016

    • Karimova, Natalia V.; Aikens, Christine M.
    • The Journal of Physical Chemistry A, Vol. 120, Issue 48
    • DOI: 10.1021/acs.jpca.6b10063

    Giant Faraday Rotation in Mesogenic Organic Molecules
    journal, March 2013

    • Vandendriessche, Stefaan; Van Cleuvenbergen, Stijn; Willot, Pieter
    • Chemistry of Materials, Vol. 25, Issue 7
    • DOI: 10.1021/cm4004118

    Longest-Wavelength Electronic Excitations of Linear Cyanines: The Role of Electron Delocalization and of Approximations in Time-Dependent Density Functional Theory
    journal, September 2013

    • Moore, Barry; Autschbach, Jochen
    • Journal of Chemical Theory and Computation, Vol. 9, Issue 11
    • DOI: 10.1021/ct400649r

    Electronic spectral studies of some uranium(V) compounds
    journal, May 1968

    • Selbin, Joel; Ortego, James D.; Gritzner, G.
    • Inorganic Chemistry, Vol. 7, Issue 5
    • DOI: 10.1021/ic50063a027

    Covalency effects on the ligand field splittings of octahedral 5f7 compounds
    journal, March 1974

    • Edelstein, N.; Brown, D.; Whittaker, B.
    • Inorganic Chemistry, Vol. 13, Issue 3
    • DOI: 10.1021/ic50133a013

    Quasi-relativistic SCF X.alpha. study of octahedral 5f1 complexes
    journal, May 1980

    • Thornton, Geoffrey; Roesch, Notker; Edelstein, Norman
    • Inorganic Chemistry, Vol. 19, Issue 5
    • DOI: 10.1021/ic50207a039

    Detailed Assignment of the Magnetic Circular Dichroism and UV−vis Spectra of Five-Coordinate High-Spin Ferric [Fe(TPP)(Cl)]
    journal, June 2008

    • Paulat, Florian; Lehnert, Nicolai
    • Inorganic Chemistry, Vol. 47, Issue 11
    • DOI: 10.1021/ic8002838

    Second-order perturbation theory with a CASSCF reference function
    journal, July 1990

    • Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O.
    • The Journal of Physical Chemistry, Vol. 94, Issue 14
    • DOI: 10.1021/j100377a012

    Spectroscopic and Computational Studies of Co 1+ Cobalamin:  Spectral and Electronic Properties of the “Superreduced” B 12 Cofactor
    journal, July 2006

    • Liptak, Mathew D.; Brunold, Thomas C.
    • Journal of the American Chemical Society, Vol. 128, Issue 28
    • DOI: 10.1021/ja061433q

    Spectroscopic and Electronic Structure Studies of a Dimethyl Sulfoxide Reductase Catalytic Intermediate: Implications for Electron- and Atom-Transfer Reactivity
    journal, June 2011

    • Mtei, Regina P.; Lyashenko, Ganna; Stein, Benjamin
    • Journal of the American Chemical Society, Vol. 133, Issue 25
    • DOI: 10.1021/ja109178q

    Outer-Sphere Contributions to the Electronic Structure of Type Zero Copper Proteins
    journal, April 2012

    • Lancaster, Kyle M.; Zaballa, María-Eugenia; Sproules, Stephen
    • Journal of the American Chemical Society, Vol. 134, Issue 19
    • DOI: 10.1021/ja302190r

    Quantifying the σ and π Interactions between U(V) f Orbitals and Halide, Alkyl, Alkoxide, Amide and Ketimide Ligands
    journal, July 2013

    • Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola
    • Journal of the American Chemical Society, Vol. 135, Issue 29
    • DOI: 10.1021/ja403815h

    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
    journal, June 2014

    • Daifuku, Stephanie L.; Al-Afyouni, Malik H.; Snyder, Benjamin E. R.
    • Journal of the American Chemical Society, Vol. 136, Issue 25
    • DOI: 10.1021/ja503596m

    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
    journal, December 1998

    • Neese, Frank; Solomon, Edward I.
    • Journal of the American Chemical Society, Vol. 120, Issue 49
    • DOI: 10.1021/ja981561h

    Iron(II) Active Species in Iron–Bisphosphine Catalyzed Kumada and Suzuki–Miyaura Cross-Couplings of Phenyl Nucleophiles and Secondary Alkyl Halides
    journal, August 2015

    • Daifuku, Stephanie L.; Kneebone, Jared L.; Snyder, Benjamin E. R.
    • Journal of the American Chemical Society, Vol. 137, Issue 35
    • DOI: 10.1021/jacs.5b06648

    Magnetic Circular Dichroism Evidence for an Unusual Electronic Structure of a Tetracarbene–Oxoiron(IV) Complex
    journal, October 2016

    • Ye, Shengfa; Kupper, Claudia; Meyer, Steffen
    • Journal of the American Chemical Society, Vol. 138, Issue 43
    • DOI: 10.1021/jacs.6b07708

    The A and B Terms of Magnetic Circular Dichroism Revisited
    journal, October 2008

    • Solheim, Harald; Ruud, Kenneth; Coriani, Sonia
    • The Journal of Physical Chemistry A, Vol. 112, Issue 40
    • DOI: 10.1021/jp803135x

    Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy
    journal, December 2016

    • Formanuik, Alasdair; Ariciu, Ana-Maria; Ortu, Fabrizio
    • Nature Chemistry, Vol. 9, Issue 6
    • DOI: 10.1038/nchem.2692

    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

    Structure–function correlations in oxygen activating non-heme iron enzymes
    journal, January 2005

    • Neidig, Michael L.; Solomon, Edward I.
    • Chemical Communications, Issue 47
    • DOI: 10.1039/b510233m

    Recent advances in computational actinoid chemistry
    journal, January 2012

    • Wang, Dongqi; van Gunsteren, Wilfred F.; Chai, Zhifang
    • Chemical Society Reviews, Vol. 41, Issue 17
    • DOI: 10.1039/c2cs15354h

    Electronic spectra and magnetic circular dichroism of the uranyl ion. Part II. The effect of reduced symmetry on the spectra
    journal, January 1974

    • Brint, Paul; McCaffery, Anthony J.
    • Journal of the Chemical Society, Dalton Transactions, Issue 1
    • DOI: 10.1039/dt9740000051

    Magnetic circular dichroism of symmetry and spin forbidden transitions of high-spin metal ions
    journal, January 2000

    • Oganesyan, Vasily S.; Thomson, Andrew J.
    • The Journal of Chemical Physics, Vol. 113, Issue 12
    • DOI: 10.1063/1.1289531

    The generalized Douglas–Kroll transformation
    journal, November 2002

    • Wolf, Alexander; Reiher, Markus; Hess, Bernd Artur
    • The Journal of Chemical Physics, Vol. 117, Issue 20
    • DOI: 10.1063/1.1515314

    Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials
    journal, January 2003

    • Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann
    • The Journal of Chemical Physics, Vol. 118, Issue 2
    • DOI: 10.1063/1.1521431

    Theory of Magnetic Circular Dichroism
    journal, January 1970

    • Stephens, P. J.
    • The Journal of Chemical Physics, Vol. 52, Issue 7
    • DOI: 10.1063/1.1673514

    Calculation of the A term of magnetic circular dichroism based on time dependent-density functional theory I. Formulation and implementation
    journal, June 2004

    • Seth, Michael; Ziegler, Tom; Banerjee, Arup
    • The Journal of Chemical Physics, Vol. 120, Issue 23
    • DOI: 10.1063/1.1747828

    Calculated optical and magnetic properties of hexafluorouranate (V) anion: UF[sub 6][sup −]
    journal, January 2004

    • Arratia-Pérez, Ramiro; Hernandez-Acevedo, Lucia; Malli, Gulzari L.
    • The Journal of Chemical Physics, Vol. 121, Issue 16
    • DOI: 10.1063/1.1799891

    Ab initio calculation of the C∕D ratio of magnetic circular dichroism
    journal, March 2005

    • Seth, Michael; Ziegler, Tom; Autschbach, Jochen
    • The Journal of Chemical Physics, Vol. 122, Issue 9
    • DOI: 10.1063/1.1856453

    Importance of vibronic effects on the circular dichroism spectrum of dimethyloxirane
    journal, June 2005

    • Neugebauer, Johannes; Jan Baerends, Evert; Nooijen, Marcel
    • The Journal of Chemical Physics, Vol. 122, Issue 23
    • DOI: 10.1063/1.1927519

    Relativistic molecular orbital study of the optical and magnetic properties of hexachloro protactinate (IV): PaCl62−
    journal, February 2006

    • Arratia-Pérez, Ramiro; Malli, Gulzari L.
    • The Journal of Chemical Physics, Vol. 124, Issue 7
    • DOI: 10.1063/1.2173251

    Calculation of the magnetic circular dichroism B term from the imaginary part of the Verdet constant using damped time-dependent density functional theory
    journal, December 2007

    • Krykunov, Mykhaylo; Seth, Michael; Ziegler, Tom
    • The Journal of Chemical Physics, Vol. 127, Issue 24
    • DOI: 10.1063/1.2806990

    First-principles calculations of magnetic circular dichroism spectra
    journal, March 2008

    • Ganyushin, Dmitry; Neese, Frank
    • The Journal of Chemical Physics, Vol. 128, Issue 11
    • DOI: 10.1063/1.2894297

    Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism: Calculation of B terms
    journal, April 2008

    • Seth, Michael; Krykunov, Mykhaylo; Ziegler, Tom
    • The Journal of Chemical Physics, Vol. 128, Issue 14
    • DOI: 10.1063/1.2901967

    Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism. II. Calculation of A terms
    journal, June 2008

    • Seth, Michael; Krykunov, Mykhaylo; Ziegler, Tom
    • The Journal of Chemical Physics, Vol. 128, Issue 23
    • DOI: 10.1063/1.2933550

    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

    Fully optimized contracted Gaussian basis sets for atoms Li to Kr
    journal, August 1992

    • Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart
    • The Journal of Chemical Physics, Vol. 97, Issue 4
    • DOI: 10.1063/1.463096

    Density‐functional thermochemistry. III. The role of exact exchange
    journal, April 1993

    • Becke, Axel D.
    • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
    • DOI: 10.1063/1.464913

    Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
    journal, May 1994

    • Küchle, W.; Dolg, M.; Stoll, H.
    • The Journal of Chemical Physics, Vol. 100, Issue 10
    • DOI: 10.1063/1.466847

    Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional
    journal, March 1999

    • Ernzerhof, Matthias; Scuseria, Gustavo E.
    • The Journal of Chemical Physics, Vol. 110, Issue 11
    • DOI: 10.1063/1.478401

    Toward reliable density functional methods without adjustable parameters: The PBE0 model
    journal, April 1999

    • Adamo, Carlo; Barone, Vincenzo
    • The Journal of Chemical Physics, Vol. 110, Issue 13
    • DOI: 10.1063/1.478522

    A fully variational spin-orbit coupled complete active space self-consistent field approach: Application to electron paramagnetic resonance g-tensors
    journal, March 2013

    • Ganyushin, Dmitry; Neese, Frank
    • The Journal of Chemical Physics, Vol. 138, Issue 10
    • DOI: 10.1063/1.4793736

    Photoelectron spectroscopy and theoretical studies of gaseous uranium hexachlorides in different oxidation states: UCl6q− (q = 0–2)
    journal, April 2015

    • Su, Jing; Dau, Phuong D.; Liu, Hong-Tao
    • The Journal of Chemical Physics, Vol. 142, Issue 13
    • DOI: 10.1063/1.4916399

    Ab initio all-electron fully relativistic Dirac—Fock self-consistent field calculations for UCI 6
    journal, January 2003


    The electronic structure of the uranyl ion: Part I. The electronic spectrum of Cs2UO2Cl4
    journal, August 1976


    The electronic structure of the uranyl ion: II. The electronic spectra of CsUO
    journal, April 1979


    The electronic structure of actinyl ions: V.
    journal, June 1982


    The electronic structure of actinyl ions: VI. Charge transfer transitions in Cs
    journal, June 1982


    Orbitals for Analyzing Bonding and Magnetism of Heavy-Metal Complexes
    journal, September 2015


    Magnetic Optical Activity
    journal, October 1966