Reactivity of Al3O3- cluster toward H2O studied by density functional theory.
Density functional theory calculations (Becke's three parameter hybrid functional) have been done on a wide range of possible structures for the complexes formed in the reaction between Al(3)O(3) (-) and one or two water molecules. Both energetically competitive structural isomers of Al(3)O(3) (-) (kitelike and distorted rectangle) were considered. The structures of neutral complexes accessed from detachment of the stable anion structures were also optimized. The calculations predict that hydroxide complexes are energetically favored over Lewis acid-base and charge-dipole complexes. For Al(3)O(3) (-)/H(2)O complexes, the kite-based hydroxide and rectangle-based hydroxide are predicted to be nearly isoenergetic, while for Al(3)O(3) (-)/(H(2)O)(2), the rectangle-based dihydroxide emerges as being 0.5 eV more stable than the lowest energy kite-based dihydroxide. The structures of these and their neutrals are used to analyze anion PE spectra of Al(3)O(4)H(2) (-) and Al(3)O(5)H(4) (-) obtained previously [F. A. Akin and C. C. Jarrold, J. Chem. Phys. 118, 5841 (2003)].
Akin
F Ahu
FA
Department of Chemistry, University of Nevada, Reno, Nevada 89557, USA. ahu@chem.unr.edu
Jarrold
Caroline Chick
CC