Ab initio study of a Bi3+ impurity in Cs2NaYCl6 and Y2O3:: Comparison of perturbative and variational electron correlation methods

Ab initio study of excitation energies and oscillator strengths for absorption towards the P-3(1) and P-1(1) states of the Bi3+ ion has been performed for the Bi3+ ion in gas phase and as a dopant of the cubic elpasolite Cs2NaYCl6 and the yttria Y2O3 crystal using the ab initio embedded-cluster method. The ground and excited states were computed with a relativistic spin-orbit configuration interaction approach suited for heavy elements. Electron correlation was treated in the scalar relativistic scheme with perturbative, variational, and coupled-cluster methods. Intermediate coupling is included via an effective-Hamiltonian based spin-orbit configuration interaction approach. Small-core (60 electrons) and large-core (78 electrons) relativistic effective core potentials (ECPs) have been used to describe the bismuth ion. The best match with experiment was obtained with the small-core ECP. The accuracy of excitation energies strongly depends on the electron correlation method used. The agreement between experimental data and the results obtained using second-order multiconfigurational perturbation theory is greatly improved with the shifted zeroth-order Hamiltonian proposed by Ghido [Chem. Phys. Lett. 396, 142 (2004)]. Although quite time consuming, coupled-cluster and variational methods yield good agreement with experimental data. The first absorption band recorded for the doped elpasolite crystal is positioned with an excellent accuracy while the computed energy of the second absorbing manifold is in poorer agreement with experimental data. This suggests that interactions with neglected close-lying excited states with a ligand-to-metal charge transfer character may be significant. Calculations of the spectrum of Bi3+ doping yttria in both the S-6 and C-2 site symmetries indicate that the absorbing manifold arises from electronic excitations localized on the Bi3+ doping ion with main triplet 6s6p character. Our results predict the first absorbing peak to lie about 0.5 eV lower for the S-6 sites than for the C-2 site, thus attributing the violet and the green emission wavelengths to the S-6 and C-2 sites, respectively. A subsequent study of Stokes shift and emission wavelength should hopefully lead to a final assignment of the measured excitation spectra. (c) 2006 American Institute of Physics.