High-resolution electron spectroscopy, preferential metal-binding sites, and thermochemistry of lithium complexes of polycyclic aromatic hydrocarbons.
Polycyclic aromatic hydrocarbons are model systems for studying the mechanisms of lithium storage in carbonaceous materials. In this work, Li complexes of naphthalene, pyrene, perylene, and coronene were synthesized in a supersonic metal-cluster beam source and studied by zero-electron-kinetic-energy (ZEKE) electron spectroscopy and density functional theory calculations. The adiabatic ionization energies of the neutral complexes and frequencies of up to nine vibrational modes in the singly charged cations were determined from the ZEKE spectra. The metal-ligand bond energies of the neutral complexes were obtained from a thermodynamic cycle. Preferred Li∕Li(+) binding sites with the aromatic molecules were determined by comparing the measured spectra with theoretical calculations. Li and Li(+) prefer the ring-over binding to the benzene ring with a higher π-electron content and aromaticity. Although the ionization energies of the Li complexes show no clear correlation with the size of the aromatic molecules, the metal-ligand bond energies increase with the extension of the π-electron network up to perylene, then decrease from perylene to coronene. The trends in the ionization and metal-ligand bond dissociation energies of the complexes are discussed in terms of the orbital energies, local quadrupole moments, and polarizabilities of the free ligands and the charge transfer between the metal atom and aromatic molecules.
Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055, USA.
Jung Sup
JS
Lee
Serge A
SA
Krasnokutski
Dong-Sheng
DS
Yang
D008094:Lithium / Q000737:chemistry*; D013058:Mass Spectrometry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
D009942:Organometallic Compounds; D011084:Polycyclic Aromatic Hydrocarbons; D008094:Lithium