Photoelectron imaging of tetrahydrofuran cluster anions (THF) n-(1≤n≤100)

Ryan M. Young, Margaret A. Yandell, Markus Niemeyer, Daniel M. Neumark

Research output: Contribution to journalArticle

12 Scopus citations

Abstract

Anionic tetrahydrofuran clusters (THF)n -(1≤n≤100) are studied with photoelectron imaging as gas-phase precursors for electrons solvated in THF. Photoelectron spectra of clusters up to n=5 show two peaks, one of which is attributed to a solvated open chain radical anion and the other to the closed THF ring. At n=6, the spectra change shape abruptly, which become more characteristic of (THF) n- clusters containing solvated electrons. From n=6-100, the vertical detachment energies (VDEs) of these solvated electron clusters increase from 1.96 to 2.71 eV, scaling linearly with n-1/3. For fully deuterated (THF-d8)-n clusters, the apparent transition to a solvated electron cluster is delayed to n=11. Extrapolation of the VDEs to infinite cluster size yields a value of 3.10 eV for the bulk photoelectric threshold. The relatively large VDEs at onset and small stabilization with increasing cluster size compared to other solvated electron clusters may reflect the tendency of the bulk solvent to form preexisting voids that can readily solvate a free electron.

Original languageEnglish (US)
Article number154312
JournalJournal of Chemical Physics
Volume133
Issue number15
DOIs
StatePublished - Oct 21 2010

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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