Do water's electrons care about electrolytes?

Pohl, Marvin Nicolas; Muchová, Eva; Seidel, Robert; Ali, Hebatallah; Sršeň, Štěpán; Wilkinson, Iain; Winter, Bernd; Slavı́ček, Petr

doi:10.1039/c8sc03381a

Cited by 40 publications

(93 citation statements)

References 145 publications

(144 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We have shown previously that in aqueous solutions a quantitative picture of the electronic structure of hydrated electrons and surrounding water molecules can be obtained using DFT−based ab initio molecular dynamics (AIMD)(44). Here we employ an extension of this Similarly to previously studied aqueous microjets (47,48), in experiments with liquid ammonia we also observe electrostatic effects leading to global PE spectral shifts. These shifts are larger for alkali metals in liquid ammonia than for solutions of alkali halide salts at equivalent concentrations (49).…”

mentioning

confidence: 99%

See 1 more Smart Citation

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

Buttersack

Mason

McMullen

et al. 2020

Science

Self Cite

View full text Add to dashboard Cite

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.

show abstract

mentioning

confidence: 99%

“…Refs. (47,48)). Nevertheless, these factors add together to produce a small systematic uncertainty in determining absolute values of VDEs, which we estimate not to exceed ~0.4 eV.…”

mentioning

confidence: 99%

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

Buttersack

Mason

McMullen

et al. 2020

Science

Self Cite

View full text Add to dashboard Cite

show abstract

“…1, with the corresponding aqueous solvent and sodium cation orbitals shown in light blue and grey, respectively. (A splitting of the H 2 O (l) 3a 1 molecular orbital due to intermolecular anti-bonding and bonding contributions, respectively 3a 1-L and 3a 1-H , 59 is indicated by a light-blue fill). The positions of the MnO 4 À (aq.)…”

Section: Resultsmentioning

confidence: 99%

The electronic structure of the aqueous permanganate ion: aqueous-phase energetics and molecular bonding studied using liquid jet photoelectron spectroscopy

Mudryk

Seidel

Winter

et al. 2020

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

“…73 Whereas interfacial effects on the photochemistry 74 and ultraviolet spectroscopy 75,76 of small aqueous solutes have been demonstrated, there has been no systematic investigation of whether VIEs themselves are sensitive to the presence of the air/water interface; the only detailed studies concern the rather unique case of the hydrated electron. 66,[77][78][79][80][81][82][83] It is known that the VIE of liquid water is largely unaffected by dissolved ions, 84 shifting by < 0.2 eV over an 8 M concentration range, 84 and the VIE of I − (aq) is similarly unaffected by concentration. 85 It is not yet known whether VIEs of aqueous ions are sensitive to the air/water interface or not.…”

Section: Introductionmentioning

confidence: 99%

Probing Interfacial Effects on Ionization Energies: The Surprising Banality of Anion-Water Hydrogen Bonding at the Air/Water Interface

Paul¹,

Herbert²

2021

Preprint

View full text Add to dashboard Cite

Liquid microjet photoelectron spectroscopy is an increasingly common technique to measure vertical ionization energies (VIEs) of aqueous solutes, although the interpretation of these experiments is subject to questions regarding sensitivity to bulk versus interfacial solvation environments. Here, we compute aqueous-phase VIEs for a set of inorganic anions, some of which partition preferentially at the air/water interface, using a combination of molecular dynamics simulations and electronic structure calculations. The results are in excellent agreement with experiment, regardless of whether the simulation data are restricted to ions at the air/water interface or to those in bulk liquid water. Although the computed VIEs are sensitive to ion-water hydrogen bonding, we find that the short-range solvation structure is sufficiently similar in the bulk and interfacial environments that it proves impossible to discriminate between the two on the basis of the VIE, a conclusion that has important implications for the interpretation of liquid-phase photoelectron spectroscopy. More generally, analysis of the simulation data suggests that partitioning of soft anions at the air/water interface is largely a second (or third) solvation shell effect, arising from disruption of water-water hydrogen bonds and not from significant changes in first-shell anion-water hydrogen bonding. <br>

show abstract

Do water's electrons care about electrolytes?

Abstract: Ions have a profound effect on the geometrical structure of liquid water and an aqueous environment is known to change the electronic structure of ions.

Cited by 40 publications

References 145 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

The electronic structure of the aqueous permanganate ion: aqueous-phase energetics and molecular bonding studied using liquid jet photoelectron spectroscopy

Probing Interfacial Effects on Ionization Energies: The Surprising Banality of Anion-Water Hydrogen Bonding at the Air/Water Interface

Contact Info

Product

Resources

About