Selectivity in Electron Attachment to Water Clusters

Lietard, Aude; Verlet, Jan R. R.

doi:10.1021/acs.jpclett.9b00275

Cited by 14 publications

(13 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“… 73 In similar experiments, various atomic and molecular species (and electrons) adsorbed on water clusters have been observed to remain on the surface. 42 , 74 − 76 …”

Section: Resultsmentioning

confidence: 99%

Core and Valence Level Photoelectron Spectroscopy of Nanosolvated KCl

et al. 2021

View full text Add to dashboard Cite

The solvation of alkali and halide ions in the aqueous environment has been a subject of intense experimental and theoretical research with multidisciplinary interests; yet, a comprehensive molecular-level understanding has still not been obtained. In recent years, electron spectroscopy has been increasingly applied to study the electronic and structural properties of aqueous ions with implications, especially in atmospheric chemistry. In this work, we report core and valence level (Cl 2p, Cl 3p, and K 3p) photoelectron spectra of the common alkali halide, KCl, doped in gas-phase water clusters in the size range of a few hundred water molecules. The results indicate that the electronic structure of these nanosolutions shows a distinct character from that observed at the liquid–vapor interface in liquid microjets and ambient pressure setups. Insights are provided into the unique solvation properties of ions in a nanoaqueous environment, emerging properties of bulk electrolyte solutions with growing cluster size, and sensitivity of the electronic structure to varying solvation configurations.

show abstract

“… 73 In similar experiments, various atomic and molecular species (and electrons) adsorbed on water clusters have been observed to remain on the surface. 42 , 74 − 76 …”

Section: Resultsmentioning

confidence: 99%

Core and Valence Level Photoelectron Spectroscopy of Nanosolvated KCl

et al. 2021

View full text Add to dashboard Cite

show abstract

“…The idea of selectivity in electron attachment was recently suggested and successfully tested experimentally for water cluster anions. 60 At the end of the paper, we underline the limitations of our approach. First, we note the approximations involved in the applied computational methods, and the limited sampling.…”

Section: Discussionmentioning

confidence: 99%

Excess electron solvation in ammonia clusters

Baranyi

Túri

2019

The Journal of Chemical Physics

View full text Add to dashboard Cite

We performed a combination of quantum chemical calculations and molecular dynamics simulations to assess the stability of various size NH3n− ammonia cluster anions up to n = 32 monomers. In the n = 3–8 size range, cluster anions are optimized and the vertical detachment energy of the excess electron (VDE) from increasing size clusters is computed using various level methods including density functional theory, MP2, and coupled-cluster singles doubles with perturbative triples. These clusters bind the electrons in nonbranched hydrogen bonding chains in dipole bound states. The VDE increases with size from a few millielectron volt up to ∼200 meV. The electron binding energy is weaker than that in water clusters but comparable to small methanol cluster VDEs. We located the first branched hydrogen bonding cluster that binds the excess electron at n = 7. For larger (n = 8–32) clusters, we generated cold, neutral clusters by semiempirical and ab initio molecular dynamics simulations and added an extra electron to selected neutral configurations. VDE calculations on the adiabatic and the relaxed anionic structures suggest that the n = 12–32 neutral clusters weakly bind the excess electron. Electron binding energies for these clusters (∼100 meV) appear to be significantly weaker than those extrapolated from experimental data. The observed excess electron states are diffuse and localized outside the molecular frame (surface states) with minor (∼1%) penetration to the nitrogen frontier orbitals. Stable minima with excess electron states surrounded by solvent molecules (cavity states) were not found in this size regime.

show abstract

“…9 Much insight has been brought by inspecting anionic molecular clusters with the increasing number of monomeric units. [10][11][12] For example, isolated water molecule does not support the existence of a stable anion, however, already a water dimer does. 13 Also, even though the binding energy of the electron gradually increases, 14 the anion signal has a strong onset only above n = 10 water molecules.…”

mentioning

confidence: 98%

Vibrationally Mediated Stabilization of Electrons in Nonpolar Matter

Med

Sršeň

Slavı́ček

et al. 2020

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

We explore solvation of electrons in non-polar matter, here represented by butadiene clusters. Isolated butadiene supports only the existence of transient anions (resonances). Two-dimensional electron energy loss spectroscopy shows that the resonances lead to an efficient vibrational excitation of butadiene, which can result into almost complete energy loss of the interacting electron. Cluster-beam experiments show that molecular clusters of butadiene form stable anions, however only at sizes larger than 9 molecular units. We have calculated the distribution of electron affinities of clusters using classical and path integral molecular dynamics simulations. There is almost a continuous transition from the resonant to the bound anions with the increasing cluster size. The comparison of the classical and quantum dynamics reveals that the electron binding is strongly supported by molecular vibrations, brought about by nuclear zero point motion and thermal agitation. We also inspected the structure of the solvated electron, finding it well localized.

show abstract

Selectivity in Electron Attachment to Water Clusters

Cited by 14 publications

References 43 publications

Core and Valence Level Photoelectron Spectroscopy of Nanosolvated KCl

Core and Valence Level Photoelectron Spectroscopy of Nanosolvated KCl

Excess electron solvation in ammonia clusters

Vibrationally Mediated Stabilization of Electrons in Nonpolar Matter

Contact Info

Product

Resources

About