Abstract

The structural, electronic and magnetic properties of Ti-13, Ti12C, V-13 and V12C clusters with octahedral (O-h), decahedral (D-5h) and icosahedral (I-h) geometries have been analyzed by means of DFT calculations as well as the adsorption of some chemical species has been performed (12CO and 12NO) onto Ti-13 (I-h) and Ti12C (I-h) clusters. The geometry energetically preferred is the icosahedron in both cases: pristine and carbide (doped with one carbon atom), for titanium and vanadium elements. The doping effect generates a transition on electronic behavior from semiconductor to metallic with respect to pristine systems for titanium clusters, whereas the vanadium clusters exhibit opposite behavior from metallic to semiconductor. The multiplicities (M = 2s + 1) remain without changes from pristine to carbide systems (excepting for octahedron), however for vanadium clusters, there is a transition M = 2 -> 1 due to substitution of central atom of these systems with respect to pristine cases. The chemisorption of nitrogen monoxide onto the Ti-13 (I-h) and Ti12C (I-h) clusters is around of two times stronger than carbon monoxide due to the high electronic charge transference from the titanium atoms of cluster surface toward the nitrogen atoms of NO molecules.