Prediction of the structures and heats of formation of MO2, MO3, and M2O5 for M = V, Nb, Ta, Pa.

Abstract

Structures for the mono-, di-, and tri-bridge isomers of M2O5 as well as those for the MO2 and MO3 fragments for M = V, Nb, Ta, and Pa were optimized at the density functional theory (DFT) level. Single point CCSD(T) calculations extrapolated to the complete basis set (CBS) limit at the DFT geometries were used to predict the energetics. The lowest energy dimer isomer was the di-bridge for M = V and Nb and the tri-bridge for M = Ta and Pa. The di-bridge isomers were predicted to be composed of MO2+ and MO3- fragments, whereas the mono- and tri-bridge are two MO2+ fragments linked by an O2-. The heats of formation of M2O5 dimers, as well as MO2 and MO3 neutral and ionic species were predicted using the Feller-Peterson-Dixon (FPD) approach. The heats of formation of the MF5 species were calculated to provide additional benchmarks. Dimerization energies to form the M2O5 dimers are predicted to become more negative going down group 5 and range from -29 to -45 kcal mol-1. The ionization energies (IEs) for VO2 and TaO2 are essentially the same at 8.75 eV whereas the IEs for NbO2 and PaO2 are 8.10 and 6.25 eV, respectively. The predicted adiabatic electron affinities (AEAs) range from 3.75 eV to 4.45 eV for the MO3 species and vertical detachment energies from 4.21 to 4.59 eV for MO3-. The calculated MO bond dissociation energies increase from 143 kcal mol-1 for M = V to ∼170 kcal mol-1 for M = Nb and Ta to ∼200 kcal mol-1 for M = Pa. The M-O bond dissociation energies are all similar ranging from 97 to 107 kcal mol-1. Natural bond analysis provided insights into the types of chemical bonds in terms of their ionic character. Pa2O5 is predicted to behave like an actinyl species dominated by the interactions of approximately linear PaO2+ groups.