Negative ions of transition metal-halogen clusters.

ABSTRACT

A systematic density functional theory based study of the structure and spectroscopic properties of neutral and negatively charged MX(n) clusters formed by a transition metal atom M (M=Sc,Ti,V) and up to seven halogen atoms X (X=F,Cl,Br) has revealed a number of interesting features (1) Halogen atoms are bound chemically to Sc, Ti, and V for n≤n(max), where the maximal valence n(max) equals to 3, 4, and 5 for Sc, Ti, and V, respectively. For n>n(max), two halogen atoms became dimerized in the neutral species, while dimerization begins at n=5, 6, and 7 for negatively charged clusters containing Sc, Ti, and V. (2) Magnetic moments of the transition metal atoms depend strongly on the number of halogen atoms in a cluster and the cluster charge. (3) The number of halogen atoms that can be attached to a metal atom exceeds the maximal formal valence of the metal atom. (4) The electron affinities of the neutral clusters abruptly rise at n=n(max), reaching values as high as 7 eV. The corresponding anions could be used in the synthesis of new salts, once appropriate counterions are identified.