Computational study of analogues of the uranyl ion containing the -N=U=N- unit: density functional theory calculations on UO2(2+), UON+, UN2, UO(NPH3)3+, U(NPH3)2(4+), [UCl4[NPR3]2] (R = H, Me), and [UOCl4[NP(C6H5)3]].

@article{Kaltsoyannis2000ComputationalSO,
title={Computational study of analogues of the uranyl ion containing the -N=U=N- unit: density functional theory calculations on UO2(2+), UON+, UN2, UO(NPH3)3+, U(NPH3)2(4+), [UCl4[NPR3]2] (R = H, Me), and [UOCl4[NP(C6H5)3]].},
author={Nikolas Kaltsoyannis},
journal={Inorganic chemistry},
year={2000},
volume={39 26},
pages={6009-17}
}

The electronic and geometric structures of the title species have been studied computationally using quasi-relativistic gradient-corrected density functional theory. The valence molecular orbital ordering of UO2(2+) is found to be pi g < pi u < sigma g << sigma u (highest occupied orbital), in agreement with previous experimental conclusions. The significant energy gap between the sigma g and sigma u orbitals is traced to the "pushing from below" mechanism: a filled-filled interaction between… CONTINUE READING