The alkali metals: 200 years of surprises

Dye, James

doi:10.1098/rsta.2014.0174

Cited by 31 publications

(30 citation statements)

References 48 publications

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“…These mixtures are highly reactive electron conductors. While there are many reports of dissolving sodium and potassium in cyclic ethers [21][22][23][24] , the possibility of dissolving lithium in ethers has, to our knowledge, not been reported. Additional work is required to establish the properties of lithium metal dissolved in PEO.…”

Section: Main Textmentioning

confidence: 97%

Dissolution of Lithium Metal in Poly(ethylene oxide)

et al. 2019

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Section: Main Textmentioning

confidence: 97%

Dissolution of Lithium Metal in Poly(ethylene oxide)

et al. 2019

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“…Our studies paint a picture of an alkalide species being far beyond a “gaslike” ion in solution, but instead one that could be “chemically” controlled and developed by considering superalkali–alkalide interactions of the sort delineated here. We believe that the interactions of alkalides in solution is merely the most recent in a long line of surprising and unique aspects of s-block chemistry 1 and certainly one that has the potential to affect how these systems are extended and applied in the future.…”

Section: Discussionmentioning

confidence: 99%

“…Anionic forms of the electropositive Group I metals, with the exception of lithium, can be generated in condensed phases. 1 Termed alkalides, these monoanions are chemically highly reducing and possess a diffuse, closed-shell n s 2 configuration, resulting in an exceptionally high electronic polarizability. The formation and stabilization of alkalide species requires stringent chemical environments and involves either a disproportionation or the reduction of one elemental alkali metal by another.…”

Section: Introductionmentioning

confidence: 99%

Superalkali–Alkalide Interactions and Ion Pairing in Low-Polarity Solvents

et al. 2021

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The nature of anionic alkali metals in solution is traditionally thought to be “gaslike” and unperturbed. In contrast to this noninteracting picture, we present experimental and computational data herein that support ion pairing in alkalide solutions. Concentration dependent ionic conductivity, dielectric spectroscopy, and neutron scattering results are consistent with the presence of superalkali–alkalide ion pairs in solution, whose stability and properties have been further investigated by DFT calculations. Our temperature dependent alkali metal NMR measurements reveal that the dynamics of the alkalide species is both reversible and thermally activated suggesting a complicated exchange process for the ion paired species. The results of this study go beyond a picture of alkalides being a “gaslike” anion in solution and highlight the significance of the interaction of the alkalide with its complex countercation (superalkali).

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“…In this study, we apply PIMC to study sodium. Na is an element that has been of wide interest [9] since it is traditionally viewed as a "simple metal" yet adopts a series of non-close-packed phases under high pressure [10], associated with changes in optical and electronic properties [11,12] and melting behavior [13,14]. It was also found that Na turns insulating at 200 GPa and re-metalizes at 15.5 TPa [15,16,17].…”

Section: Introductionmentioning

confidence: 99%

Path integral Monte Carlo simulations of warm dense sodium

Zhang

Driver

Soubiran

et al. 2016

High Energy Density Physics

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High energy density physics and astrophysics require reliable methods for determining the equation of state of warm dense matter. At high temperatures (above 10 6 K or 100 eV), path integral Monte Carlo (PIMC) as a first-principles method is a useful option because of its accuracy and efficiency. Previous developments in PIMC implemented free-particle nodes to study plasmas comprised of heavy (Z ≤ 10) elements, and constructed equations of state in tandem with those from molecular dynamics (MD) simulations based on density functional theory (DFT), whose applicability is limited to low temperatures (up to ∼10 6 K). Recent PIMC method developments employed a localized, Hartree-Fock nodal surface, allowing for a better description of bound states in warm dense silicon. In this work, we use the localized nodal scheme to study warm dense sodium. We demonstrate that PIMC and DFT-MD produce a coherent equation of state, and discuss the electronic structure of the plasma.

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The alkali metals: 200 years of surprises

Abstract: One contribution of 18 to a discussion meeting issue 'The new chemistry of the elements' .

Cited by 31 publications

References 48 publications

Dissolution of Lithium Metal in Poly(ethylene oxide)

Dissolution of Lithium Metal in Poly(ethylene oxide)

Superalkali–Alkalide Interactions and Ion Pairing in Low-Polarity Solvents

Path integral Monte Carlo simulations of warm dense sodium

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