1 Department of Physics, Chemistry and Pharmacy, Faculty of Science, SDU2 ETH Zuerich3 Vrije Universitet Amsterdam4 Universite Paul Sabatier Toulouse5 Department of Physics, Chemistry and Pharmacy, Faculty of Science, SDU
The electrostatic contribution to the Mössbauer isomer shift of mercury for the series HgFn (n = 1, 2; 4) with respect to the neutral atom has been investigated in the framework of 4- and 2-component relativistic theory. Replacing the integration of the electron density over the nuclear volume by the contact density (that is, the electron density at the nucleus) leads to a 10% overestimation of the isomer shift. The systematic nature of this error suggests that it can be incorporated into a correction factor, thus justifying the use of the contact density for the calculation of the Mössbauer isomer shift. The performance of a large selection of density functionals for the calculation of contact densities has been assessed by comparing with finite-field 4-component relativistic Coupled-Cluster with Single and Double and Perturbative Triple excitations [CCSD(T)] calculations. For the absolute contact density of the mercury atom the Density Functional Theory (DFT) calculations are in error by about 0.5%, a result which must be judged against the observation that the change in contact density along the series HgFn (n = 1; 2; 4), relevant for the isomer shift, is on the order of 50 ppm with respect to absolute densities. Contrary to previous studies of the 57Fe isomer shift [F. Neese, Inorg. Chim. Acta 332 (2002) 181], for mercury DFT is not able to reproduce the trends in the isomer shift provided by reference data, in our case CCSD(T) calculations, notably the non-monotonous decrease in the contact density along the series HgFn (n = 1; 2; 4). Projection analysis shows the expected reduction of the 6s1/2 population at the mercury center with an increasing number of ligands, but also brings into light an opposing effect, namely the increasing polarization of the 6s1/2 orbital due to increasing eective charge of the mercury atom, which explains the non-monotonous behavior of the contact density along the series. The same analysis shows increasing covalent contributions to bonding along the series with the eective charge of the mercury atom reaching a maximum of around +2 for HgF4 at the DFT level, far from the formal charge +4 suggested by the oxidation state of this recently observed species. Whereas the geometries for the linear HgF2 and square-planar HgF4 molecules were taken from previous computational studies, we optimized the equilibrium distance of HgF at the 4-component Fock-space CCSD/aug-cc-pVQZ level, giving spectroscopic constants re = 2.007 Å and ωe = 513.5 cm-1.
Theoretical Chemistry Accounts, 2011, Vol 129, Issue 3-5, p. 631-650