PFI-ZEKE PHOTOELECTRON SPECTROSCOPY OF ALKALI METAL-ETHER COMPLEXES

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Title: PFI-ZEKE PHOTOELECTRON SPECTROSCOPY OF ALKALI METAL-ETHER COMPLEXES
Creators: Sohnlein, Bradford R.; Fuller, Jason F.; Li, Shenggang; Yang, Dong-Sheng
Issue Date: 2004
Publisher: Ohio State University
Abstract: This talk will present the PFI-ZEKE photoelectron spectra of two alkali metal-ether complexes: Li(DME) and Li(DXE); $DME = CH_{3}OCH_{3}, DXE = CH_{3}O(CH_{2})_{2}OCH_{3}$. Both complexes were produced in a pulsed molecular beam and identified by time-of-flight mass spectrometry. The ZEKE spectra of these complexes show adiabatic ionization potentials and vibrational structures consisting of metal-ligand and ligand-based vibrations. The spectroscopic measurements were combined with density functional theory and Franck-Condon factor calculations to establish ground electronic states and geometries of the neutral and ionic species. For Li(DME), the neutral and ionic complexes were determined to be in $C_{2v}$ symmetry with Li binding to oxygen. For Li(DXE), the Li atom binds to both oxygen atoms in a $C_{2}$ five-membered ring structure, with the O-C-C-O dihedral angle of ${\sim}50^{\circ}$ in both the ion and neutral species. The ground electronic states of the DME complex and its ion are ${^{2}}A_{1}$ and ${^{1}}A_{1}$, whereas those of the corresponding DXE complex and its ion are $^{2}A_{1}$ and $^{1}A$, respectively. Furthermore, the binding energies of the two neutral complexes were derived using a thermodynamic cycle. This simple calculation requires the ionization energies of the metal atom and complex as well as the dissociation energy of the cation complex.
Description: Author Institution: Department of Chemistry, University of Kentucky
URI: http://hdl.handle.net/1811/21156
Other Identifiers: 2004-FC-02
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