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| - Two-Dimensional Penning Ionization Electron Spectroscopy of CH2ClI and CH2ClCN
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| - The electronic structures of CH2ClI and CH2ClCN and anisotropic interactions with the metastable He*(23S)atoms are studied by two-dimensional (electron-energy and collision-energy-resolved) Penning ionizationelectron spectroscopy as well as He I ultraviolet photoelectron spectroscopy. A broad band with the highionization potentials in the Penning ionization electron spectrum of CH2ClI is proposed to be related toautoionizations of the Cl** or I** species produced through dissociations after the excitation transfer fromthe He* atom. The split bands having the characteristics of the Cl and I lone pair electrons (nCl and nI) areobserved in the spectra, as being interpreted by the intramolecular orbital (nCl ↔ nI and nCl ↔ πCN) through-space/through-bond interactions rather than the spin−orbit coupling effects. The magnitude of intramolecularorbital nCl ↔ πCN interactions is much stronger than that of the nCl ↔ nI interactions. The collision energydependence of partial Penning ionization cross sections is interpreted on the basis of the delocalizedcharacteristics of the electron distributions for respective molecular orbitals and the model calculations of theinteraction potential energies.
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