Relativistic molecular orbital study of the optical and magnetic properties of hexachloro protactinate (IV): PaCl6(2-).
Our ab initio all-electron Dirac-Fock and the corresponding nonrelativistic limit calculations performed at four Pa-Cl bond distances yield for octahedral PaCl(6) (2-) the optimized Pa-Cl bond distances of 2.758 and 2.771 Angstroms, respectively. Dirac scattered wave and its nonrelativistic limit calculations are performed at the optimized Pa-Cl bond distances using a first-order perturbation procedure to obtain the molecular g and hyperfine tensors for the octahedral anion PaCl(6) (2-). The calculated Zeeman and (231)Pa hyperfine interactions are in fairly good agreement with the electron paramagnetic resonance and electron nuclear double resonance values of the Pa(4+) impurity site in the octahedral Cs(2)ZrCl(6) lattice. The calculated relativistic transition energies of the 5f-->5f and 5f-->6d absorption bands are also in good agreement with the experimental results.
Departamento de Ciencias Químicas, Universidad Andrés Bello, Santiago, Chile. rarratia@unab.ci
Ramiro
R
Arratia-Pérez
Gulzari L
GL
Malli