DFT calculations on group 5 mixed metal tetramers: TaxNbyVz (x+y+z=4)

Abstract

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We report Density Functional Theory (DFT) calculations on mixed-metal tetramers comprised of the Group 5 (Vb) elements V, Nb, and Ta. Our results show that the lowest energy structures for Nb4 and Ta4 are regular tetrahedra with Td symmetry and singlet multiplicity whereas V4 is a triplet state with C2v symmetry. The monosubstituted isomers, A3B, all have C3v symmetry but several higher energy Cs structures have been found that are approximately 100 kJ mol−1 higher in energy. The disubstituted isomers all posses arachno-butterfly structures; the A2B2 types with C2v symmetry and the A2BC types with Cs symmetry. However, the relative openness of the arachno structures is found to be specific to the composition of the mixed-metal cluster. </jats:p>