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 MO 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.