TY - JOUR
T1 - Two-dimensional penning ionization electron spectroscopy of adamantanes and cyclohexanes
T2 - Electronic structure of adamantane, 1-chloroadamantane, cyclohexane, and chlorocyclohexane and interaction potential with He*(23S)
AU - Tian, Shan Xi
AU - Kishimoto, Naoki
AU - Ohno, Koichi
PY - 2002/7/18
Y1 - 2002/7/18
N2 - The electronic structures of adamantane, 1-chloroadamantane, cyclohexane, and chlorocyclohexane and their interaction potentials with He*(23S) metastable atoms are studied by two-dimensional (collision- and electron-energy-resolved) Penning ionization electron spectroscopy and model potential calculations. The model potential calculations are performed for the target-Li system based on a well-known resemblance between a metastable excited He*(23S) atom and a ground-state Li(22S) atom. Assignments of the electron spectra are made on the basis of ab initio and outer-valence Green's function calculations. Strong repulsive interactions between the saturated hydrocarbons and the metastable atom and strength sequence σCC > σCH observed experimentally are consistent with the anisotropic potential calculations. It is noted that attractive interaction in the region where lone-pair nCl electrons are distributed for 1-chloroadamantane is weaker than that for chlorocyclohexane, because of the stronger steric shielding effect by the larger adamantane skeleton. Through comparison with the previous results on the saturated chloro-hydrocarbons, we find that the attractive interaction around the nCl electron distribution does not become stronger as the energy level of the highest occupied molecular orbital becomes higher, which is the result of competition between effects of low exterior electron distributions and high energy levels.
AB - The electronic structures of adamantane, 1-chloroadamantane, cyclohexane, and chlorocyclohexane and their interaction potentials with He*(23S) metastable atoms are studied by two-dimensional (collision- and electron-energy-resolved) Penning ionization electron spectroscopy and model potential calculations. The model potential calculations are performed for the target-Li system based on a well-known resemblance between a metastable excited He*(23S) atom and a ground-state Li(22S) atom. Assignments of the electron spectra are made on the basis of ab initio and outer-valence Green's function calculations. Strong repulsive interactions between the saturated hydrocarbons and the metastable atom and strength sequence σCC > σCH observed experimentally are consistent with the anisotropic potential calculations. It is noted that attractive interaction in the region where lone-pair nCl electrons are distributed for 1-chloroadamantane is weaker than that for chlorocyclohexane, because of the stronger steric shielding effect by the larger adamantane skeleton. Through comparison with the previous results on the saturated chloro-hydrocarbons, we find that the attractive interaction around the nCl electron distribution does not become stronger as the energy level of the highest occupied molecular orbital becomes higher, which is the result of competition between effects of low exterior electron distributions and high energy levels.
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U2 - 10.1021/jp014302e
DO - 10.1021/jp014302e
M3 - Article
AN - SCOPUS:0037130519
VL - 106
SP - 6541
EP - 6553
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 28
ER -