Metal Transition in Sodium–Ammonia Nanodroplets

Hartweg, Sebastian; West, Adam H. C.; Yoder, Bruce L.; Signorell, Ruth

doi:10.1002/anie.201604282

Cited by 13 publications

(19 citation statements)

References 43 publications

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“…Early photoelectron total emission yield experiments led to an estimate of the photoelectron threshold of about 1.4 eV (24,25), in good agreements with electrochemical determination of the adiabatic binding energy of an ammoniated electron (26). This value is also roughly consistent with results from cluster extrapolations (27)(28)(29)(30)(31). However, clusters have only limited relevance to the liquid bulk systems, as they inevitably exhibit large surface effects and are typically solid rather than liquid (32,33); as a result, e.g., metastable cluster structures exist, characterized by low electron binding energies, which have no liquid bulk analogue (33), and also electron scattering from clusters differs from condensed phase data (34).…”

supporting

confidence: 83%

Photoelectron spectra of alkali metal–ammonia microjets: From blue electrolyte to bronze metal

Buttersack

Mason

McMullen

et al. 2020

Science

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Experimental studies of the electronic structure of excess electrons in liquids—archetypal quantum solutes—have been largely restricted to very dilute electron concentrations. We overcame this limitation by applying soft x-ray photoelectron spectroscopy to characterize excess electrons originating from steadily increasing amounts of alkali metals dissolved in refrigerated liquid ammonia microjets. As concentration rises, a narrow peak at ~2 electron volts, corresponding to vertical photodetachment of localized solvated electrons and dielectrons, transforms continuously into a band with a sharp Fermi edge accompanied by a plasmon peak, characteristic of delocalized metallic electrons. Through our experimental approach combined with ab initio calculations of localized electrons and dielectrons, we obtain a clear picture of the energetics and density of states of the ammoniated electrons over the gradual transition from dilute blue electrolytes to concentrated bronze metallic solutions.

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supporting

confidence: 83%

Photoelectron spectra of alkali metal–ammonia microjets: From blue electrolyte to bronze metal

Buttersack

Mason

McMullen

et al. 2020

Science

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“…64) Der terminale Phosphinidenkomplex von Mangan, [(η 5 -C 5 H 5 ) -(OC) 2 Mn= PN (Mes*) B (tBu) Cl], entsteht durch Zugeben von ClPNMes* zum terminalen Borylenkomplex [(η 5 -C 5 H 5 ) (OC) 2 Mn= -B tBu]. 65) Die dreifache Funktionalisierung von Phosphan mit NIiPr (NIiPr = 1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidenamino) führt zu P(NIiPr) 3 , einen bei Raumtemperatur stabilen Feststoff, der mit CO 2 ein Addukt bildet. 66 86) In (95) liegen die Xenonatome in der Oxidationsstufe +II vor, und die ermittelten Xe-N-Einfachbindungen sind die kürzesten, die bislang zwischen einem sp-hybridisierten Stickstoff-und einem Xenonatom bekannt sind.…”

Section: Tetreleunclassified

Anorganische Chemie 2016: Hauptgruppenelemente

Kammerer¹,

Böttcher²

2017

Nachr. Chem.

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Hauptgruppenelemente: Alkalimetalle in Wasser beim Explodieren gefilmt, das erste Germavinyliden, ein neues Polysulfat, und elementare Halogene bilden als Lewis‐Basen Addukte. Koordinationschemie: Beryllium(0)‐Verbindungen, Bor wechselt zwischen +I und +III, Kubas‐artige Komplexverbindungen aus zinkorganischen Verbindungen und Übergangsmetallen. Bioanorganik: [Mn4V4O17(OAc)3]3– verhält sich wie der Oxygen Evolving Cluster des Photosystems II, ein [Fe]‐Hydrogenasemodell, das H2 direkt aktiviert, und Eisenkomplexe generieren aus N2 bis zu 64 Äquivalente Ammoniak pro Eisenzentrum.

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“…This illustrates that the localized and delocalized electron states do not readily co‐exist, which is dramatically manifested by the fact that the more concentrated metallic solution floats above the dilute electrolytic phase for T < T c . Above 8 MPM the solutions do not exhibit phase separation, appearing golden up to the concentration limit of 20 MPM, the expanded metal Li(NH 3 ) 4 . The concentration and temperature dependence of this liquid–liquid phase separation has been mapped through multi‐element NMR spectroscopy …”

Section: Figurementioning

confidence: 99%

Electron Solvation and the Unique Liquid Structure of a Mixed‐Amine Expanded Metal: The Saturated Li–NH₃–MeNH₂ System

et al. 2017

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Metal-amine solutions provideaunique arena in which to study electrons in solution, and to tune the electron density from the extremes of electrolytic through to true metallic behavior.The existence and structure of anew class of concentrated metal-amine liquid, Li-NH 3 -MeNH 2 ,i sp resented in which the mixed solvent produces an ovel type of electron solvation and delocalization that is fundamentally different from either of the constituent systems.N MR, ESR, and neutron diffraction allowt he environment of the solvated electron and liquid structure to be precisely interrogated. Unexpectedly it was found that the solution is truly homogeneous and metallic.Equally surprising was the observation of strong longer-range order in this mixed solvent system. This is despite the heterogeneity of the cation solvation, and it is concluded that the solvated electron itself acts as as tructural template.This is aquite remarkable observation, given that the liquid is metallic.Alkali metals demonstrate an exceptional solubility in NH 3 , yielding intensely colored conducting solutions that have fascinated chemists since the time of Sir Humphry Davy. [1,2] Va rying the concentration of metal in these liquids dramatically alters the electronic,magnetic,and structural properties of the solutions,a nd enables us to experimentally determine the manner in which liquid systems accommodate excess electron density.A talow concentration of metal/electrons, the solutions are electrolytic, whereby the metal valence electrons have been ionized into solution and exist as solvated electrons propagating between solvent cavities.[3] Increasing the concentration results in metallization in the liquid phase, which for the Li À NH 3 system occurs at amere 4mol %metal (MPM).[2] Interestingly at lower temperatures,b elow T C = 210 K, the point of the Mott-type metal-insulator transition (MIT) is obscured by ap ronounced liquid-liquid phase separation.[2] This illustrates that the localized and delocalized electron states do not readily co-exist, which is dramatically manifested by the fact that the more concentrated metallic solution floats above the dilute electrolytic phase for T < T c .[2,4] Above 8MPM the solutions do not exhibit phase separation, appearing golden up to the concentration limit of 20 MPM, [5] thee xpanded metal Li(NH 3 ) 4 . [6,7] Thec oncentration and temperature dependence of this liquid-liquid phase separation has been mapped through multi-element NMR spectroscopy. [8] Along with metal concentration, chemical tunability of the electronic properties of these systems can be achieved by varying the amine.L ithium will also dissolve in MeNH 2 to yield as ystem whereby solvated electrons transition to am etallic state. [3,[9][10][11][12] TheM IT in Li-MeNH 2 occurs at 15 MPM, an otably higher concentration than in Li-NH 3 . No liquid-liquid phase separation has been detected across the full concentration range of Li-MeNH 2 ,a nd the solution remains ad eep blue,a lbeit with am etallic luster. The conductivity of liqui...

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Metal Transition in Sodium–Ammonia Nanodroplets

Cited by 13 publications

References 43 publications

Photoelectron spectra of alkali metal–ammonia microjets: From blue electrolyte to bronze metal

Photoelectron spectra of alkali metal–ammonia microjets: From blue electrolyte to bronze metal

Anorganische Chemie 2016: Hauptgruppenelemente

Electron Solvation and the Unique Liquid Structure of a Mixed‐Amine Expanded Metal: The Saturated Li–NH₃–MeNH₂ System

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Metal Transition in Sodium–Ammonia Nanodroplets

Cited by 13 publications

References 43 publications

Photoelectron spectra of alkali metal–ammonia microjets: From blue electrolyte to bronze metal

Photoelectron spectra of alkali metal–ammonia microjets: From blue electrolyte to bronze metal

Anorganische Chemie 2016: Hauptgruppenelemente

Electron Solvation and the Unique Liquid Structure of a Mixed‐Amine Expanded Metal: The Saturated Li–NH3–MeNH2 System

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Electron Solvation and the Unique Liquid Structure of a Mixed‐Amine Expanded Metal: The Saturated Li–NH₃–MeNH₂ System