Theoretical Investigation of Actinide Ligation in Aqueous and Organic Phase for Nuclear Waste Treatment

Laub, Jeffrey A; Vogiatzis, Konstantinos D.

doi:10.1021/acs.jpca.2c08828

Cited by 3 publications

(1 citation statement)

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“…With very few exceptions of (almost) nonempirical XCFs, − such approximations have parameters fitted to reproduce mostly light-element data. Hence, these XCFs’ transferability to modeling heavy-element chemistry with significant relativistic effects cannot be guaranteed and requires careful evaluation. − Furthermore, Aebersold and Wilson demonstrate that deficiencies in XCFs’ performance are heavily entangled with those of the basis sets. Surprisingly, there are very few classes of basis sets developed explicitly for DFT, − with even fewer − available for heavy elements: for example, polarization-consistent (pc) basis sets − cover elements H through Kr only.…”

Section: Introductionmentioning

confidence: 99%

Novel Computational Chemistry Infrastructure for Simulating Astatide in Water: From Basis Sets to Force Fields Using Particle Swarm Optimization

Rueda Espinosa,

Kananenka,

Rusakov

2023

J. Chem. Theory Comput.

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Using the example of astatine, the heaviest naturally occurring halogen whose isotope At-211 has promising medical applications, we propose a new infrastructure for large-scale computational models of heavy elements with strong relativistic effects. In particular, we focus on developing an accurate force field for At– in water based on reliable relativistic density functional theory (DFT) calculations. To ensure the reliability of such calculations, we design novel basis sets for relativistic DFT, via the particle swarm optimization algorithm to optimize the coefficients of the new basis sets and the polarization-consistent basis set idea’s extension to heavy elements to eliminate the basis set error from DFT calculations. The resulting basis sets enable the well-grounded evaluation of relativistic DFT against “gold-standard” CCSD(T) results. Accounting for strong relativistic effects, including spin–orbit interaction, via our redesigned infrastructure, we elucidate a noticeable dissimilarity between At– and I– in halide–water force field parameters, radial distribution functions, diffusion coefficients, and hydration energies. This work establishes the framework for the systematic development of polarization-consistent basis sets for relativistic DFT and accurate force fields for molecular dynamics simulations to be used in large-scale models of complex molecular systems with elements from the bottom of the periodic table, including actinides and even superheavy elements.

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