Abstract
The extended <TEX>$H{\ddot{u}}ckel$</TEX> method is employed to analyze the interaction of carbon monoxide with the TiC(001) surfaces, both perfect and containing carbon vacancies. CO exhibits a similar <TEX>${\sigma}$</TEX>-donation interaction for both <TEX>$Ti_{25}C_{25}$</TEX> and <TEX>$Ti_{25}C_{23}$</TEX> clusters, as deduced from the fact that the populations of the CO <TEX>$5{\sigma}$</TEX> orbital are identical upon adsorption, but it bonds more strongly with the <TEX>$Ti_{25}C_{23}$</TEX> than with the <TEX>$Ti_{25}C_{25}$</TEX> because the metal d electron density in <TEX>$Ti_{25}C_{23}$</TEX> provides <TEX>${\pi}$</TEX> back-bonding interactions with CO that are absent in <TEX>$Ti_{25}C_{25}$</TEX>. This work suggests that a difference in reactivity toward CO of stoichiometric TiC and TiC with carbon defects is connected with the occupancy of <TEX>$2{\pi}^*$</TEX> orbitals that leads to a significant weakening of the C-O bond.
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