Collisions of sodium atoms with liquid glycerol

Insights into solvation and ionization

Justin P. Wiens, Gilbert M. Nathanson, William A. Alexander, Timothy K. Minton, Sankaran Lakshmi, George C Schatz

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The reactive uptake and ionization of sodium atoms in glycerol were investigated by gas-liquid scattering experiments and ab initio molecular dynamics (AIMD) simulations. A nearly effusive beam of Na atoms at 670 K was directed at liquid glycerol in vacuum, and the scattered Na atoms were detected by a rotatable mass spectrometer. The Na velocity and angular distributions imply that all impinging Na atoms that thermally equilibrate on the surface remain behind, likely ionizing to e- and Na+. The reactive uptake of Na atoms into glycerol was determined to be greater than 75%. Complementary AIMD simulations of Na striking a 17-molecule glycerol cluster indicate that the glycerol hydroxyl groups reorient around the Na atom as it makes contact with the cluster and begins to ionize. Although complete ionization did not occur during the 10 ps simulation, distinct correlations among the extent of ionization, separation between Na+ and e -, solvent coordination, and binding energies of the Na atom and electron were observed. The combination of experiments and simulations indicates that Na-atom deposition provides a low-energy pathway for generating solvated electrons in the near-interfacial region of protic liquids.

Original languageEnglish
Pages (from-to)3065-3074
Number of pages10
JournalJournal of the American Chemical Society
Volume136
Issue number8
DOIs
Publication statusPublished - Feb 26 2014

Fingerprint

Solvation
Glycerol
Ionization
Sodium
Atoms
Liquids
Molecular Dynamics Simulation
Electrons
Molecular dynamics
Vacuum
Hydroxyl Radical
Gases
Angular distribution
Computer simulation
Mass spectrometers
Velocity distribution
Binding energy
Experiments
Scattering
Molecules

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Collisions of sodium atoms with liquid glycerol : Insights into solvation and ionization. / Wiens, Justin P.; Nathanson, Gilbert M.; Alexander, William A.; Minton, Timothy K.; Lakshmi, Sankaran; Schatz, George C.

In: Journal of the American Chemical Society, Vol. 136, No. 8, 26.02.2014, p. 3065-3074.

Research output: Contribution to journalArticle

Wiens, Justin P. ; Nathanson, Gilbert M. ; Alexander, William A. ; Minton, Timothy K. ; Lakshmi, Sankaran ; Schatz, George C. / Collisions of sodium atoms with liquid glycerol : Insights into solvation and ionization. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 8. pp. 3065-3074.
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