Metal Oxide Reactions in Complex Environments: High Electric Fields and Pressures above Ultrahigh Vacuum Page: 15
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that cooperative effects strongly favor molecules with hydrogen bond (HB) patterns in
which each molecule is simultaneously a proton donor and an acceptor of HBs [86, 87].
The cooperative surface interaction is particularly relevant to alumina surface
chemistry since molecular dynamics (MD) studies [88] indicate that cooperative surface
reactions involving several H20 molecules may be responsible for the surface
hydroxylation observed at high pressures. UHV, which is required to keep atomically
Outermost cations have large inward
relaxation The cations are shielded by
large anions
Surface is nominally Al3 oxygen atoms
terminated, but
Al+3 ions
Fig. 1.2. Alumina surface in UHV: relaxation of surface cations reduces reactivity.
clean surfaces, however, precludes observation of many cooperative surface interactions,
as the following rough calculation shows. From the kinetic theory of gases, the flux (F) of
molecules to the surfaces (in terms of atoms/cm2.sec) at a given pressure P is [16]:
F = 3.51 x 1022 P(torr) (1-7)
M (g / mole)T
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Qin, Feili. Metal Oxide Reactions in Complex Environments: High Electric Fields and Pressures above Ultrahigh Vacuum, dissertation, August 2005; Denton, Texas. (https://digital.library.unt.edu/ark:/67531/metadc4843/m1/26/?rotate=90: accessed July 17, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; .