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 language | English (US) |
|---|---|
| Article number | 154312 |
| Journal | Journal of Chemical Physics |
| Volume | 133 |
| Issue number | 15 |
| DOIs | |
| State | Published - Oct 21 2010 |
Funding
This work was supported by the National Science Foundation (CHE-0649647). R.M.Y. is grateful to the Samuel Ruben/Irv Fatt Fellowship, and M.A.Y. was supported by DoD, Air Force Office of Scientific Research, National Defense Science and Engineering Graduate (NDSEG) Fellowship, 32 CFR 168a. The authors are also grateful to Tara Yacovitch for her help with the ab initio calculations, and to Dr. Oli Ehrler for his advice and assistance in building our new data acquisition program.
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry