Dissecting the cation–cation interaction between two uranyl units

Tecmer, Paweł; Hong, Sung Wook; Boguslawski, Katharina

doi:10.1039/c6cp03542f

Cited by 15 publications

(23 citation statements)

References 57 publications

(134 reference statements)

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“…[23][24][25][26][27][28] Furthermore, neptunyl ions can form small oligomeric or polymeric clusters that are known as cation-cation interactions (CCIs). [29][30][31][32][33] This characteristic, albeit peculiar behaviour was first observed for neptunium(V) in uranyl perchlorate solution and aqueous chlorate media. [34][35][36] The stability of CCI complexes depends on the composition of the solution.…”

Section: Introductionmentioning

confidence: 92%

Elucidating cation–cation interactions in neptunyl dications using multi-referenceab initiotheory

Lachmanska

Tecmer

Legeza

et al. 2019

Phys. Chem. Chem. Phys.

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Understanding the binding mechanism in neptunyl clusters formed due to cation-cation interactions is of crucial importance in nuclear waste reprocessing and related areas of research. Since experimental manipulations with such species are often rather limited, we have to rely on quantumchemical predictions of their electronic structures and spectroscopic parameters. In this work, we present a state-of-the-art quantum chemical study of the T-shaped and diamond-shaped neptunyl(V) and neptunyl(VI) dimers. Specifically, we scrutinize their molecular structures, (implicit and explicit) solvation effects, the interplay of static and dynamical correlation, and the influence of spin-orbit coupling on the ground state and lowest-lying excited states for different total spin states and total charges of the neptunyl dications. Furthermore, we use the picture of interacting orbitals (quantum entanglement and correlation analysis) to identify strongly correlated orbitals in the cation-cation complexes that should be included in complete active space calculations. Most importantly, our study highlights the complex interplay of correlation effects and relativistic corrections in the description of the ground and lowest-lying excited states of neptunyl dications.

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Section: Introductionmentioning

confidence: 92%

Elucidating cation–cation interactions in neptunyl dications using multi-referenceab initiotheory

Lachmanska

Tecmer

Legeza

et al. 2019

Phys. Chem. Chem. Phys.

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“…In rare cases, a uranyl oxo atom can bond to a neighboring uranyl through the equatorial plane [116]. Historically, this is described as a cation-cation interaction and was previously shown to perturb the uranyl bond [116,117]. Cation-cation interactions cause the uranyl bond engaged in this interaction to weaken and the ν 1 band to red shift.…”

Section: Chemical and Structural Elucidation Of Uranium Solid-state Cmentioning

confidence: 99%

“…Vibrational analysis provides additional information regarding the unusual coordination environment of uranium within inorganic or mineral phases. In rare cases, a uranyl oxo atom can bond to a neighboring uranyl through the equatorial plane [116]. Historically, this is described as a cation-cation interaction and was previously shown to perturb the uranyl bond [116,117].…”

Section: Chemical and Structural Elucidation Of Uranium Solid-state Cmentioning

confidence: 99%

Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy

Haes

Forbes

2018

Coordination Chemistry Reviews

129

128

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The purpose of this review is to provide an overview of uranium speciation using vibrational spectroscopy methods including Raman and IR. Uranium is a naturally occurring, radioactive element that is utilized in the nuclear energy and national security sectors. Fundamental uranium chemistry is also an active area of investigation due to ongoing questions regarding the participation of 5f orbitals in bonding, variation in oxidation states and coordination environments, and unique chemical and physical properties. Importantly, uranium speciation affects fate and transportation in the environment, influences bioavailability and toxicity to human health, controls separation processes for nuclear waste, and impacts isotopic partitioning and geochronological dating. This review article provides a thorough discussion of the vibrational modes for U(IV), U(V), and U(VI) and applications of infrared absorption and Raman scattering spectroscopies in the identification and detection of both naturally occurring and synthetic uranium species in solid and solution states. The vibrational frequencies of the uranyl moiety, including both symmetric and asymmetric stretches are sensitive to the coordinating ligands and used to identify individual species in water, organic solvents, and ionic liquids or on the surface of materials. Additionally, vibrational spectroscopy allows for the in situ detection and real-time monitoring of chemical reactions involving uranium. Finally, techniques to enhance uranium species signals with vibrational modes are discussed to expand the application of vibrational spectroscopy to biological, environmental, inorganic, and materials scientists and engineers.

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“…. From the data available in the literature,64,105,[109][110][111][112][113][114] we can estimate that the ranges for the optimal bond length are 1.67-1.72 Å for UO 2+…”

mentioning

confidence: 99%

Assessing the accuracy of simplified coupled cluster methods for electronic excited states in f0 actinide compounds

Nowak

Tecmer

Boguslawski

2019

Phys. Chem. Chem. Phys.

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We scrutinize the performance of different variants of equation of motion coupled cluster (EOM-CC) methods to predict electronic excitation energies and excited state potential energy surfaces in closedshell actinide species. We focus our analysis on various recently presented pair coupled cluster doubles (pCCD) models [J. Chem. Phys., 23, 234105 (2016) and J. Chem. Theory Comput. 15, 18-24 (2019)] and compare their performance to the conventional EOM-CCSD approach and to the completely renormalized EOM-CCSD with perturbative triples ansatz. Since the single-reference pCCD model allows us to efficiently describe static/nondynamic electron correlation, while dynamical electron correlation is accounted for a posteriori, the investigated pCCD-based methods represent a good compromise between accuracy and computational cost. Such a feature is particularly advantageous when modelling electronic structures of actinide-containing compounds with stretched bonds. Our work demonstrates that EOM-pCCD-based methods reliably predict electronic spectra of small actinide building blocks containing thorium, uranium, and protactinium atoms. Specifically, the standard errors in adiabatic and vertical excitation energies obtained by the conventional EOM-CCSD approach are reduced by a factor of 2 when employing the EOM-pCCD-LCCSD variant resulting in a mean error of 0.05 eV and a standard deviation of 0.25 eV.

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Dissecting the cation–cation interaction between two uranyl units

Cited by 15 publications

References 57 publications

Elucidating cation–cation interactions in neptunyl dications using multi-referenceab initiotheory

Elucidating cation–cation interactions in neptunyl dications using multi-referenceab initiotheory

Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy

Assessing the accuracy of simplified coupled cluster methods for electronic excited states in f0 actinide compounds

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