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{pi} and {sigma}-coordinated Al in AlC{sub 2}{sup {minus}} and AlCSi{sup {minus}}. A combined photoelectron spectroscopy and ab initio study

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja992102z· OSTI ID:20013682
Vibrationally resolved photoelectron spectroscopy is combined with ab initio calculations to investigate the structure and chemical bonding in AlC{sub 2}{sup {minus}} and AlCSi{sup {minus}} was found to have a C{sub 2v} structure whereas AlCSi{sup {minus}} was found to be almost linear, thus establishing {pi}-coordination of Al in AlC{sub 2}{sup {minus}} and {sigma}-coordination in AlCSi{sup {minus}}. The adiabatic electron affinities of AlC{sub 2} and AlCSi were measured to be 2.65(3) and 2.50(6) eV, respectively. The calculated vertical (2.87 eV) and adiabatic (2.60 eV) electron detachment energies for AlC{sub 2}{sup {minus}} agree well with the 2.73(0.03) and 2.65(0.03) eV experimental values, respectively. The calculated (2.86 eV) and experimental (2.64 {+-} 0.04 eV) vertical detachment energies for AlCSi{sup {minus}} were also in good agreement. The calculated vibrational frequency for AlC{sub 2}| and vertical detachment energies for other higher energy features in both AlC{sub 2}{sup {minus}} and AlCSi{sup {minus}} were also in good agreement with the experimental measurements. The combined experimental and theoretical effort allows them to elucidate the structures of AlC{sub 2}{sup {minus}} and AlCSi{sup {minus}} and the nature of their chemical bonding.
Research Organization:
Univ. of Utah, Salt Lake City, UT (US); Utah State Univ., Logan, UT (US)
Sponsoring Organization:
National Science Foundation; US Department of Energy
DOE Contract Number:
AC06-76RL01830
OSTI ID:
20013682
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 43 Vol. 121; ISSN JACSAT; ISSN 0002-7863
Country of Publication:
United States
Language:
English

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