Global and local approaches to population analysis: Bonding patterns in superheavy element compounds

Oleynichenko, Alexander V.; Zaitsevskii, Andréi; Romanov, Stepan A.; Skripnikov, L. V.; Титов, А. В.

doi:10.1016/j.cplett.2018.01.058

Cited by 15 publications

(12 citation statements)

References 26 publications

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“…Our reference RDFT calculations employ the PBE0 15,16 XCF approximation, which is (almost) free of empirically fitted parameters and has already demonstrated its reliability in heavy-and superheavy-element molecular modeling. 23,24,52,53 Based on the R e for each molecule, we generate a set of internuclear separations to model the potential energy surface within a ±0.5 Å range of R e with a 0.1 Å step. We also utilize these grids for scanning the energy curves with coupled-cluster and RDFT methods.…”

Section: Relativistic Density Functional Theory Calculationsmentioning

confidence: 99%

Investigating the Heaviest Halogen: Lessons Learned from Modeling the Electronic Structure of Astatine's Small Molecules

Rusakov

Casetti

MacLean

et al. 2022

Preprint

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We present a systematic study of electron-correlation and relativistic effects in diatomic molecular species of the heaviest halogen astatine (At) within relativistic single- and multi-reference coupled-cluster approaches and relativistic density functional theory. We establish revised reference \textit{ab initio} data for the ground states of \ce{At2}, \ce{HAt}, \ce{AtAu}, and \ce{AtO+} using a highly accurate relativistic effective core potential model and in-house basis sets developed for accurate modeling of molecules with large spin-orbit effects. Spin-dependent relativistic effects on chemical bonding in the ground state are comparable to the binding energy or even exceed it in \ce{At2}. Electron-correlation effects near the equilibrium internuclear separation are mostly dynamical and can be adequately captured using single-reference CCSD(T). However, bond elongation in \ce{At2} and, especially, \ce{AtO+} results in rapid manifestation of its multi-reference character. While useful for evaluating the spin-orbit effects on the ground-state bonding and properties, the two-component density functional theory lacks predictive power, especially in combination with popular empirically adjusted exchange-correlation functionals. This drawback supports the necessity to develop new functionals for reliable quantum-chemical models of heavy-element compounds with strong relativistic effects.

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Section: Relativistic Density Functional Theory Calculationsmentioning

confidence: 99%

Investigating the Heaviest Halogen: Lessons Learned from Modeling the Electronic Structure of Astatine's Small Molecules

Rusakov

Casetti

MacLean

et al. 2022

Preprint

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“…Recent experimental and theoretical work has focused on the formation of compounds including superheavy elements (Eichler et al, 2016;Oleynichenko et al, 2018;Ilias ˇ& Pershina, 2017;Even et al, 2014;Hammou et al, 2019). For example, a Seaborgium molecule (Z = 106) Sg(CO) 6 has been detected in the gas phase.…”

Section: Superheavy Elements Up To Z = 138mentioning

confidence: 99%

Advanced calculations of X-ray spectroscopies with FEFF10 and Corvus

Kas¹,

Vila²,

Pemmaraju³

et al. 2021

J Synchrotron Rad

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The real-space Green's function code FEFF has been extensively developed and used for calculations of X-ray and related spectra, including X-ray absorption (XAS), X-ray emission (XES), inelastic X-ray scattering, and electron energy-loss spectra. The code is particularly useful for the analysis and interpretation of the XAS fine-structure (EXAFS) and the near-edge structure (XANES) in materials throughout the periodic table. Nevertheless, many applications, such as non-equilibrium systems, and the analysis of ultra-fast pump–probe experiments, require extensions of the code including finite-temperature and auxiliary calculations of structure and vibrational properties. To enable these extensions, we have developed in tandem a new version FEFF10 and new FEFF-based workflows for the Corvus workflow manager, which allow users to easily augment the capabilities of FEFF10 via auxiliary codes. This coupling facilitates simplified input and automated calculations of spectra based on advanced theoretical techniques. The approach is illustrated with examples of high-temperature behavior, vibrational properties, many-body excitations in XAS, super-heavy materials, and fits of calculated spectra to experiment.

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“…Recent experimental and theoretical work has focused on the formation of compounds including superheavy elements [51][52][53][54][55] . For example, a Seaborgium molecule (Z = 106) Sg(CO) 6 has been detected in gas phase.…”

Section: E Superheavy Elements Up To Z = 138mentioning

confidence: 99%

Advanced calculations of x-ray spectroscopies with FEFF10 and Corvus

Kas¹,

Vila²,

Rehr³

et al. 2021

Preprint

View full text Add to dashboard Cite

The real-space Green's function code FEFF has been extensively developed and used for calculations of x-ray and related spectra, including x-ray absorption (XAS), x-ray emission (XES), inelastic x-ray scattering, and electron energy loss spectra (EELS). The code is particularly useful for the analysis and interpretation of the XAS fine-structure (EXAFS) and the near-edge structure (XANES) in materials throughout the periodic table. Nevertheless, many applications, such as non-equilibrium systems, and the analysis of ultra-fast pump-probe experiments, require extensions of the code including finite-temperature and auxiliary calculations of structure and vibrational properties. To enable these extensions, we have developed in tandem, a new version FEFF10, and new FEFF based workflows for the Corvus workflow manager, which allow users to easily augment the capabilities of FEFF10 via auxiliary codes. This coupling facilitates simplified input and automated calculations of spectra based on advanced theoretical techniques. The approach is illustrated with examples of high temperature behavior, vibrational properties, many-body excitations in XAS, super-heavy materials, and fits of calculated spectra to experiment.

show abstract

Global and local approaches to population analysis: Bonding patterns in superheavy element compounds

Cited by 15 publications

References 26 publications

Investigating the Heaviest Halogen: Lessons Learned from Modeling the Electronic Structure of Astatine's Small Molecules

Investigating the Heaviest Halogen: Lessons Learned from Modeling the Electronic Structure of Astatine's Small Molecules

Advanced calculations of X-ray spectroscopies with FEFF10 and Corvus

Advanced calculations of x-ray spectroscopies with FEFF10 and Corvus

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