231 research outputs found
CO adsorption on neutral iridium clusters
The adsorption of carbon monoxide on neutral iridium clusters in the size
range of n = 3 to 21 atoms is investigated with infrared multiple photon
dissociation spectroscopy. For each cluster size only a single v(CO) band is
present with frequencies in the range between 1962 cm-1 (n = 8) and 1985 cm-1
(n = 18) which can be attributed to an atop binding geometry. This behaviour is
compared to the CO binding geometries on clusters of other group 9 and 10
transition metals as well as to that on extended surfaces. The preference of Ir
for atop binding is rationalized by relativistic effects on the electronic
structure of the later 5d metals
First-principles extrapolation method for accurate CO adsorption energies on metal surfaces
We show that a simple first-principles correction based on the difference
between the singlet-triplet CO excitation energy values obtained by DFT and
high-level quantum chemistry methods yields accurate CO adsorption properties
on a variety of metal surfaces.
We demonstrate a linear relationship between the CO adsorption energy and the
CO singlet-triplet splitting, similar to the linear dependence of CO adsorption
energy on the energy of the CO 2* orbital found recently {[Kresse {\em et
al.}, Physical Review B {\bf 68}, 073401 (2003)]}. Converged DFT calculations
underestimate the CO singlet-triplet excitation energy ,
whereas coupled-cluster and CI calculations reproduce the experimental . The dependence of on is used
to extrapolate for the top, bridge and hollow sites for the
(100) and (111) surfaces of Pt, Rh, Pd and Cu to the values that correspond to
the coupled-cluster and CI value. The correction
reproduces experimental adsorption site preference for all cases and obtains
in excellent agreement with experimental results.Comment: Table sent as table1.eps. 3 figure
Adsorption of CO on a Platinum (111) surface - a study within a four-component relativistic density functional approach
We report on results of a theoretical study of the adsorption process of a
single carbon oxide molecule on a Platinum (111) surface. A four-component
relativistic density functional method was applied to account for a proper
description of the strong relativistic effects. A limited number of atoms in
the framework of a cluster approach is used to describe the surface. Different
adsorption sites are investigated. We found that CO is preferably adsorbed at
the top position.Comment: 23 Pages with 4 figure
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