Winter, M. J. Chemical Bonding 2nd edn (Oxford Univ. Press, 2016).Aspinall, H. C. f-Block Chemistry (Oxford Univ. Press, 2020).Kaltsoyannis, N. Does covalency increase or decrease across the actinide series? Implications for minor actinide partitioning. Inorg. Chem. 52, 3407–3413 (2013).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Neidig, M. L., Clark, D. L. & Martin, R. L. Covalency in f-element complexes. Coord. Chem. Rev. 257, 394–406 (2013).ArticleÂ
CASÂ
Google ScholarÂ
Kaltsoyannis, N. Transuranic computational chemistry. Chem. Eur. J. 24, 2815–2825 (2018).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Kerridge, A. Quantification of f-element covalency through analysis of the electron density: insights from simulation. Chem. Commun. 53, 6685–6695 (2017).ArticleÂ
CASÂ
Google ScholarÂ
Su, J. et al. Energy-degeneracy-driven covalency in actinide bonding. J. Am. Chem. Soc. 140, 17977–17984 (2018).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Lu, E. et al. Emergence of the structure-directing role of f-orbital overlap-driven covalency. Nat. Commun. 10, 634 (2019).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Taylor, R. J. (ed.) Reprocessing and Recycling of Spent Nuclear Fuel (Elsevier, 2015).Chandrasekar, A. & Ghanty, T. K. Uncovering heavy actinide covalency: implications for minor actinide partitioning. Inorg. Chem. 58, 3744–3753 (2019).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Oher, H. et al. Influence of the first coordination of uranyl on its luminescence properties: a study of uranyl binitrate with N,N-dialkyl amide DEHiBA and water. Inorg. Chem. 61, 890–901 (2022).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Tolu, D., Guillaumont, D. & de la Lande, A. Irradiation of plutonium tributyl phosphate complexes by ionizing alpha particles: a computational study. J. Phys. Chem. A 127, 7045–7057 (2023).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Fletcher, L. S. et al. Next-generation 3,3-alkoxyBTPs as complexants for minor actinide separation from lanthanides: a comprehensive separations, spectroscopic, and DFT study. Inorg. Chem. 63, 4819–4827 (2024).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Streit, M. & Ingold, F. Nitrides as a nuclear fuel option. J. Eur. Ceram. Soc. 25, 2687–2692 (2005).ArticleÂ
CASÂ
Google ScholarÂ
King, D. M. et al. Isolation and characterization of a uranium(VI)-nitride triple bond. Nat. Chem. 5, 482–488 (2013).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Jones, S., Boxall, C., Maher, C. & Taylor, R. A review of the reprocessability of uranium nitride based fuels. Prog. Nucl. Energy 165, 104917 (2023).ArticleÂ
CASÂ
Google ScholarÂ
Jensen, F. Introduction to Computational Chemistry 3rd edn (Wiley, 2016).Kaltsoyannis, N., Hay, P. J., Li, J., Blaudeau, J.-P. & Bursten, B. E. in The Chemistry of the Actinide and Transactinide Elements 3rd edn (eds Morss, L. R. et al.) 1893–2012 (Springer, 2006).Kaltsoyannis, N. & Kerridge, A. in The Chemical Bond: Fundamental Aspects of Chemical Bonding (eds Frenking, G. & Shaik, S.) 337–356 (Wiley-VCH, 2014).Hayton, T. W. & Kaltsoyannis, N. in Experimental and Theoretical Approaches to Actinide Chemistry (eds Gibson, J. K. & de Jong, W. A.) 181–236 (Wiley, 2018).Hohenberg, P. & Kohn, W. Inhomogeneous electron gas. Phys. Rev. 136, B864–B871 (1964).ArticleÂ
Google ScholarÂ
Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).ArticleÂ
Google ScholarÂ
Runge, E. & Gross, E. K. U. Density-functional theory for time-dependent systems. Phys. Rev. Lett. 52, 997–1000 (1984).ArticleÂ
CASÂ
Google ScholarÂ
Casida, M. E. in Recent Developments and Applications of Modern Density Functional Theory (ed. Seminario, J. M.) 391–439 (Elsevier, 1996).ČÞek, J. On correlation problem in atomic and molecular systems. Calculation of wavefunction components in Ursell-type expansion using quantum-field theoretical methods. J. Chem. Phys. 45, 4256–4266 (1966).ArticleÂ
Google ScholarÂ
Löwdin, P. O. Quantum theory of many-particle systems. 1. Physical interpretations by means of density matrices, natural spin-orbitals, and convergence problems in the method of configurational interaction. Phys. Rev. 97, 1474–1489 (1955).ArticleÂ
Google ScholarÂ
Roos, B. O., Taylor, P. R. & Siegbahn, P. E. M. A complete active space SCF method (CASSCF) using a density-matrix formulated super-CI approach. Chem. Phys. 48, 157–173 (1980).ArticleÂ
CASÂ
Google ScholarÂ
Malmqvist, P. A., Rendell, A. & Roos, B. O. The restricted active space self-consistent-field method, implemented with a split graph unitary-group approach. J. Phys. Chem. 94, 5477–5482 (1990).ArticleÂ
CASÂ
Google ScholarÂ
de Groot, F. Multiplet effects in X-ray spectroscopy. Coord. Chem. Rev. 249, 31–63 (2005).ArticleÂ
Google ScholarÂ
Atanasov, M. et al. First principles approach to the electronic structure, magnetic anisotropy and spin relaxation in mononuclear 3d-transition metal single molecule magnets. Coord. Chem. Rev. 289, 177–214 (2015).ArticleÂ
Google ScholarÂ
Jung, J. L., Atanasov, M. & Neese, F. Ab initio ligand-field theory analysis and covalency trends in actinide and lanthanide free ions and octahedral complexes. Inorg. Chem. 56, 8802–8816 (2017).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Ungur, L. & Chibotaru, L. F. Ab initio crystal field for lanthanides. Chem. Eur. J. 23, 3708–3718 (2017).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Autschbach, J. Orbitals: some fiction and some facts. J. Chem. Educ. 89, 1032–1040 (2012).ArticleÂ
CASÂ
Google ScholarÂ
Glendening, E. D. & Weinhold, F. Natural resonance theory: II. Natural bond order and valency. J. Comput. Chem. 19, 610–627 (1998).ArticleÂ
CASÂ
Google ScholarÂ
Weinhold, F. & Landis, C. R. Discovering Chemistry with Natural Bond Orbitals (Wiley, 2012).Martin, R. L. Natural transition orbitals. J. Chem. Phys. 118, 4775–4777 (2003).ArticleÂ
CASÂ
Google ScholarÂ
Wiberg, K. B. Application of Pople-Santry-Segal complete neglect of differential overlap method to some hydrocarbons and their cations. J. Am. Chem. Soc. 90, 59–63 (1968).ArticleÂ
CASÂ
Google ScholarÂ
Mayer, I. Charge, bond order and valence in the ab initio SCF theory. Chem. Phys. Lett. 97, 270–274 (1983).ArticleÂ
CASÂ
Google ScholarÂ
Bader, R. F. W. Atoms in Molecules: A Quantum Theory (Clarendon, 1990).Tassell, M. J. & Kaltsoyannis, N. Covalency in AnCp4 (An = Th–Cm): a comparison of molecular orbital, natural population and atoms-in-molecules analyses. Dalton Trans. 39, 6719–6725 (2010).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Kirker, I. & Kaltsoyannis, N. Does covalency really increase across the 5f series? A comparison of molecular orbital, natural population, spin and electron density analyses of AnCp3 (An = Th–Cm; Cp = η5-C5H5). Dalton Trans. 40, 124–131 (2011).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Blanco, M. A., Pendás, A. M. & Francisco, E. Interacting quantum atoms: a correlated energy decomposition scheme based on the quantum theory of atoms in molecules. J. Chem. Theory Comput. 1, 1096–1109 (2005).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Cho, H., de Jong, W. A. & Soderquist, C. Z. Probing the oxygen environment in UO22+ by solid-state 17O nuclear magnetic resonance spectroscopy and relativistic density functional calculations. J. Chem. Phys. 132, 084501 (2010).ArticleÂ
PubMedÂ
Google ScholarÂ
Martel, L. et al. High-resolution solid-state oxygen-17 NMR of actinide-bearing compounds: an insight into the 5f chemistry. Inorg. Chem. 53, 6928–6933 (2014).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Martel, L. et al. Insight into the crystalline structure of ThF4 with the combined use of neutron diffraction, 19F magic-angle spinning-NMR, and density functional theory calculations. Inorg. Chem. 57, 15350–15360 (2018).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
DeVore, M. A., Klug, C. A., Kriz, M. R., Roy, L. E. & Wellons, M. S. Investigations of uranyl fluoride sesquihydrate (UO2F2•1.57H2O): combining 19F solid-state MAS NMR spectroscopy and GIPAW chemical shift calculations. J. Phys. Chem. A 122, 6873–6878 (2018).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Fernández-Alarcón, A. & Autschbach, J. Relativistic density functional NMR tensors analyzed with spin-free localized molecular orbitals. ChemPhysChem 24, e202200667 (2023).ArticleÂ
PubMedÂ
Google ScholarÂ
Hrobárik, P., Hrobáriková, V., Greif, A. H. & Kaupp, M. Giant spin–orbit effects on NMR shifts in diamagnetic actinide complexes: guiding the search of uranium(VI) hydride complexes in the correct spectral range. Angew. Chem. Int. Ed. 51, 10884–10888 (2012).ArticleÂ
Google ScholarÂ
Seaman, L. A. et al. A rare uranyl(VI)-alkyl ate complex [Li(DME)1.5]2[UO2(CH2SiMe3)4] and its comparison with a homoleptic uranium(VI)-hexaalkyl. Angew. Chem. Int. Ed. 52, 3259–3263 (2013).ArticleÂ
CASÂ
Google ScholarÂ
Fortier, S., Walensky, J. R., Wu, G. & Hayton, T. W. High-valent uranium alkyls: evidence for the formation of UVI(CH2SiMe3)6. J. Am. Chem. Soc. 133, 11732–11743 (2011).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Panetti, G. B. et al. Isolation and characterization of a covalent CeIV-Aryl complex with an anomalous 13C chemical shift. Nat. Commun. 12, 1713 (2021).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Smiles, D. E., Wu, G., Hrobárik, P. & Hayton, T. W. Use of 77Se and 125Te NMR spectroscopy to probe covalency of the actinide-chalcogen bonding in Th(En){N(SiMe3)2}3− (E = Se, Te; n = 1, 2) and their oxo-uranium(VI) congeners. J. Am. Chem. Soc. 138, 814–825 (2016).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Ramsey, N. F. Magnetic shielding of nuclei in molecules. Phys. Rev. 78, 699–703 (1950).ArticleÂ
CASÂ
Google ScholarÂ
Smiles, D. E., Wu, G., Hrobárik, P. & Hayton, T. W. Synthesis, thermochemistry, bonding, and 13C NMR chemical shift analysis of a phosphorano-stabilized carbene of thorium. Organometallics 36, 4519–4524 (2017).ArticleÂ
CASÂ
Google ScholarÂ
Wu, W. et al. Molecular thorium compounds with dichalcogenide ligands: synthesis, structure, 77Se NMR study, and thermolysis. Inorg. Chem. 57, 14821–14833 (2018).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Mullane, K. C. et al. 13C NMR shifts as an indicator of U–C bond covalency in uranium(VI) acetylide complexes: an experimental and computational study. Inorg. Chem. 58, 4152–4163 (2019).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Staun, S. L., Sergentu, D. C., Wu, G., Autschbach, J. & Hayton, T. W. Use of 15N NMR spectroscopy to probe covalency in a thorium nitride. Chem. Sci. 10, 6431–6436 (2019).ArticleÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Sergentu, D. C. et al. Probing the electronic structure of a thorium nitride complex by solid-state 15N NMR spectroscopy. Inorg. Chem. 59, 10138–10145 (2020).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Du, J. Z. et al. Exceptional uranium(VI)-nitride triple bond covalency from 15N nuclear magnetic resonance spectroscopy and quantum chemical analysis. Nat. Commun. 12, 5649 (2021).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Berryman, V. E. J. et al. Quantum chemical topology and natural bond orbital analysis of M–O covalency in M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np). Phys. Chem. Chem. Phys. 22, 16804–16812 (2020).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Réant, B. L. L. et al. 29Si NMR spectroscopy as a probe of s- and f-block metal(II)–silanide bond covalency. J. Am. Chem. Soc. 143, 9813–9824 (2021).ArticleÂ
PubMedÂ
Google ScholarÂ
Du, J. Z. et al. 31P nuclear magnetic resonance spectroscopy as a probe of thorium–phosphorus bond covalency: correlating phosphorus chemical shift to metal–phosphorus bond order. J. Am. Chem. Soc. 145, 21766–21784 (2023).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Hedman, B., Hodgson, K. O. & Solomon, E. I. X-Ray absorption-edge spectroscopy of ligands bound to open-shell metal ions: chlorine K-edge studies of covalency in tetracholorocuprate(2−). J. Am. Chem. Soc. 112, 1643–1645 (1990).ArticleÂ
CASÂ
Google ScholarÂ
Sergentu, D. C. & Autschbach, J. X-ray absorption spectra of f-element complexes: insight from relativistic multiconfigurational wavefunction theory. Dalton Trans. 51, 1754–1764 (2022).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Kozimor, S. A. et al. Trends in covalency for d- and f-element metallocene dichlorides identified using chlorine K-edge X-ray absorption spectroscopy and time-dependent density functional theory. J. Am. Chem. Soc. 131, 12125–12136 (2009).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Kozimor, S. A. et al. Covalency trends in group IV metallocene dichlorides. Chlorine K-edge X-ray absorption spectroscopy and time dependent-density functional theory. Inorg. Chem. 47, 5365–5371 (2008).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Minasian, S. G. et al. New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory. Chem. Sci. 5, 351–359 (2014).ArticleÂ
CASÂ
Google ScholarÂ
Qiao, Y. S. et al. Enhanced 5f-δ bonding in [U(C7H7)2]−: C K-edge XAS, magnetism, and ab initio calculations. Chem. Commun. 57, 9562–9565 (2021).ArticleÂ
CASÂ
Google ScholarÂ
Gourier, D., Caurant, D., Arliguie, T. & Ephritikhine, M. EPR and angle-selected ENDOR study of 5f–ligand interactions in the [U(η7-C7H7)2]− anion, an f1 analogue of uranocene. J. Am. Chem. Soc. 120, 6084–6092 (1998).ArticleÂ
CASÂ
Google ScholarÂ
Dolg, M. et al. Formally tetravalent cerium and thorium compounds: a configuration interaction study of cerocene Ce(C8H8)2 and thorocene Th(C8H8)2 using energy-adjusted quasirelativistic ab initio pseudopotentials. Chem. Phys. 195, 71–82 (1995).ArticleÂ
CASÂ
Google ScholarÂ
Booth, C. H., Walter, M. D., Daniel, M., Lukens, W. W. & Andersen, R. A. Self-contained Kondo effect in single molecules. Phys. Rev. Lett. 95, 267202 (2005).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Kerridge, A., Coates, R. & Kaltsoyannis, N. Is cerocene really a Ce(III) compound? All-electron spin–orbit coupled CASPT2 calculations on M(η8-C8H8)2 (M = Th, Pa, Ce). J. Phys. Chem. A 113, 2896–2905 (2009).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Moossen, O. & Dolg, M. Two interpretations of the cerocene electronic ground state. Chem. Phys. Lett. 594, 47–50 (2014).ArticleÂ
CASÂ
Google ScholarÂ
Smiles, D. E. et al. The duality of electron localization and covalency in lanthanide and actinide metallocenes. Chem. Sci. 11, 2796–2809 (2020).ArticleÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Sergentu, D. C., Booth, C. H. & Autschbach, J. Probing multiconfigurational states by spectroscopy: the cerium XAS L3-edge puzzle. Chem. Eur. J. 27, 7239–7251 (2021).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Hitchcock, P. B., Lappert, M. F., Maron, L. & Protchenko, A. V. Lanthanum does form stable molecular compounds in the +2 oxidation state. Angew. Chem. Int. Ed. 47, 1488–1491, (2008).ArticleÂ
CASÂ
Google ScholarÂ
MacDonald, M. R., Ziller, J. W. & Evans, W. J. Synthesis of a crystalline molecular complex of Y2+, [(18-crown-6)K][(C5H4SiMe3)3Y]. J. Am. Chem. Soc. 133, 15914–15917 (2011).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
MacDonald, M. R. et al. Expanding rare-earth oxidation state chemistry to molecular complexes of holmium(II) and erbium(II). J. Am. Chem. Soc. 134, 8420–8423 (2012).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Ryan, A. J. et al. Synthesis, structure, and magnetism of tris(amide) [Ln{N(SiMe3)2}3]1− complexes of the non-traditional +2 lanthanide ions. Chem. Eur. J. 24, 7702–7709 (2018).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Fieser, M. E. et al. Evaluating the electronic structure of formal LnII ions in LnII(C5H4SiMe3)31− using XANES spectroscopy and DFT calculations. Chem. Sci. 8, 6076–6091 (2017).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Denning, R. G. et al. Covalency in the uranyl ion: a polarized X-ray spectroscopic study. J. Chem. Phys. 117, 8008–8020 (2002).ArticleÂ
CASÂ
Google ScholarÂ
Stanistreet-Welsh, K. & Kerridge, A. Bounding [AnO2]2+ (An = U, Np) covalency by simulated O K-edge and An M-edge X-ray absorption near-edge spectroscopy. Phys. Chem. Chem. Phys. 25, 23753–23760 (2023).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Misael, W. A. & Gomes, A. S. P. Core excitations of uranyl in Cs2UO2Cl4 from relativistic embedded damped response time-dependent density functional theory calculations. Inorg. Chem. 62, 11589–11601 (2023).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Spencer, L. P. et al. Tetrahalide complexes of the [U(NR)2]2+ ion: synthesis, theory, and chlorine K-edge X-ray absorption spectroscopy. J. Am. Chem. Soc. 135, 2279–2290 (2013).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Minasian, S. G. et al. Determining relative f and d orbital contributions to M–Cl covalency in MCl62− (M = Ti, Zr, Hf, U) and UOCl5− using Cl K-edge X-ray absorption spectroscopy and time-dependent density functional theory. J. Am. Chem. Soc. 134, 5586−5597 (2012).ArticleÂ
PubMedÂ
Google ScholarÂ
Kramers, H. A. & Heisenberg, W. On the dispersal of radiation by atoms. Z. Phys. 31, 681–708 (1925).ArticleÂ
CASÂ
Google ScholarÂ
Caciuffo, R. & Lander, G. H. X-ray synchrotron radiation studies of actinide materials. J. Synchrotron Radiat. 28, 1692–1708 (2021).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Polly, R., Schacherl, B., Rothe, J. & Vitova, T. Relativistic multiconfigurational ab initio calculation of uranyl 3d4f resonant inelastic X-ray scattering. Inorg. Chem. 60, 18764–18776 (2021).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Vitova, T. et al. The role of the 5f valence orbitals of early actinides in chemical bonding. Nat. Commun. 8, 16053 (2017).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Ehrman, J. N. et al. Unveiling hidden shake-up features in the uranyl M4-edge spectrum. JACS Au 4, 1134–1141 (2024).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Sergentu, D. C. & Autschbach, J. Covalency in actinide(IV) hexachlorides in relation to the chlorine K-edge X-ray absorption structure. Chem. Sci. 13, 3194–3207 (2022).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Cross, J. N. et al. Covalency in americium(III) hexachloride. J. Am. Chem. Soc. 139, 8667–8677 (2017).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Diamond, R. M., Street, K. & Seaborg, G. T. An ion-exchange study of possible hybridized 5f bonding in the actinides. J. Am. Chem. Soc. 76, 1461–1469 (1954).ArticleÂ
CASÂ
Google ScholarÂ
Löble, M. W. et al. Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6x− (x =3, 2). J. Am. Chem. Soc. 137, 2506–2523 (2015).ArticleÂ
PubMedÂ
Google ScholarÂ
Palumbo, C. T., Zivkovic, I., Scopelliti, R. & Mazzanti, M. Molecular complex of Tb in the +4 oxidation state. J. Am. Chem. Soc. 141, 9827–9831 (2019).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Rice, N. T. et al. Design, isolation, and spectroscopic analysis of a tetravalent terbium complex. J. Am. Chem. Soc. 141, 13222–13233 (2019).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Willauer, A. R. et al. Accessing the +IV oxidation state in molecular complexes of praseodymium. J. Am. Chem. Soc. 142, 5538–5542 (2020).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Ramanathan, A. et al. Chemical design of electronic and magnetic energy scales of tetravalent praseodymium materials. Nat. Commun. 14, 3134 (2023).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Minasian, S. G. et al. Quantitative evidence for lanthanide-oxygen orbital mixing in CeO2, PrO2, and TbO2. J. Am. Chem. Soc. 139, 18052–18064 (2017).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Kvashnina, K. O., Butorin, S. M., Martin, P. & Glatzel, P. Chemical state of complex uranium oxides. Phys. Rev. Lett. 111, 253002 (2013).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Kvashnina, K. O., Kvashnin, Y. O. & Butorin, S. M. Role of resonant inelastic X-ray scattering in high-resolution core-level spectroscopy of actinide materials. J. Electron Spectros. Relat. Phenomena 194, 27–36 (2014).ArticleÂ
CASÂ
Google ScholarÂ
Amidani, L. et al. Probing the local coordination of hexavalent uranium and the splitting of 5f orbitals induced by chemical bonding. Inorg. Chem. 60, 16286–16293 (2021).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Minasian, S. G., Krinsky, J. L. & Arnold, J. Evaluating f-element bonding from structure and thermodynamics. Chem. Eur. J. 17, 12234–12245 (2011).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Kelley, M. P. et al. Bond covalency and oxidation state of actinide ions complexed with therapeutic chelating agent 3,4,3-LI(1,2-HOPO). Inorg. Chem. 57, 5352–5363 (2018).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Formanuik, A. et al. Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy. Nat. Chem. 9, 578–583 (2017).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Schweiger, A. & Jeschke, J. Principles of Pulsed Electron Paramagnetic Resonance (Oxford Univ. Press, 2001).Nodaraki, L. E. et al. Metal–carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy. Chem. Sci. 15, 3003–3010 (2024).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Lukens, W. W. et al. The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study. Dalton Trans. 45, 11508–11521 (2016).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Wolford, N. J., Radovic, A. & Neidig, M. L. C-Term magnetic circular dichroism (MCD) spectroscopy in paramagnetic transition metal and f-element organometallic chemistry. Dalton Trans. 50, 416–428 (2021).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Wolford, N. J., Yu, X. J., Bart, S. C., Autschbach, J. & Neidig, M. L. Ligand effects on electronic structure and bonding in U(III) coordination complexes: a combined MCD, EPR and computational study. Dalton Trans. 49, 14401–14410 (2020).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Gendron, F. et al. Magnetic circular dichroism of UCl6− in the ligand-to-metal charge-transfer spectral region. Phys. Chem. Chem. Phys. 19, 17300–17313 (2017).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Notter, F. P. & Bolvin, H. Optical and magnetic properties of the 5f1 AnX6q− series: a theoretical study. J. Chem. Phys. 130, 184310 (2009).ArticleÂ
PubMedÂ
Google ScholarÂ
Fleischauer, V. E. et al. Insight into the electronic structure of formal lanthanide(II) complexes using magnetic circular dichroism spectroscopy. Organometallics 38, 3124–3131 (2019).ArticleÂ
CASÂ
Google ScholarÂ
MacDonald, M. R., Bates, J. E., Ziller, J. W., Furche, F. & Evans, W. J. Completing the series of +2 ions for the lanthanide elements: synthesis of molecular complexes of Pr2+, Gd2+, Tb2+, and Lu2+. J. Am. Chem. Soc. 135, 9857–9868, (2013).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Aquino, F., Pritchard, B. & Autschbach, J. Scalar relativistic computations and localized orbital analyses of nuclear hyperfine coupling and paramagnetic NMR chemical shifts. J. Chem. Theory Comput. 8, 598–609 (2012).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Autschbach, J. in Annual Reports in Computational Chemistry Vol. 11 (ed. Dixon, D. A.) 3–36 (Elsevier, 2015).Gendron, F. & Autschbach, J. Ligand NMR chemical shift calculations for paramagnetic metal complexes: 5f1 vs 5f2 actinides. J. Chem. Theory Comput. 12, 5309–5321 (2016).ArticleÂ
CASÂ
PubMedÂ
Google ScholarÂ
Bolvin, H. in Computational Modelling of Molecular Nanomagnets (ed. Rajaraman, G.) 179–218 (Springer, 2023).Ashuiev, A. et al. Geometry and electronic structure of Yb(III)[CH(SiMe3)2]3 from EPR and solid-state NMR augmented by computations. Phys. Chem. Chem. Phys. 26, 8734–8747 (2024).ArticleÂ
CASÂ
PubMedÂ
PubMed CentralÂ
Google ScholarÂ
Hermann, J. et al. Ab initio quantum chemistry with neural-network wavefunctions. Nat. Rev. Chem. 7, 692–709 (2023).ArticleÂ
PubMedÂ
Google ScholarÂ