First-principle calculations on the microscopic 57Fe electric-field-gradient tensor of ferrous chloride tetrahydrate: a prototypical Mössbauer species.

Since the pioneering work on the theoretical description of Mössbauer quadrupole line intensities for a single-crystal to elucidate information on the electric-field-gradient (EFG) tensor, ferrous chloride tetrahydrate, FeCl(2)·4H(2)O, has represented a prototypical Mössbauer species. In addition, this species also typifies a so-called ambiguous, low symmetry, iron center where traditionally only macroscopic tensors have been assumed available for determination. Recent experiments on FeCl(2)·4H(2)O have successfully determined physically meaningful spin-Hamiltonian parameters for the (57)Fe microscopic (local) EFG and mean-squared displacement tensors. This paper reports a density functional theory investigation that finds good agreement with experiment. Assuming a gas-phase scaffold cluster approach to describe the crystalline geometry, the sign of the EFG was determined to be positive, in agreement with earlier magnetically perturbed experiments, and the EFG asymmetry parameter η was calculated to be 0.21-0.23 depending on the density functional used, which is in excellent accord with experiment at 0.25(2). By virtue of theoretical and experimental agreement, this work indicates that simultaneous electric-field-gradient-mean-square-displacement Mössbauer determinations can resolve the apparent ambiguity associated with monoclinic, 2/m or 1 Laue class, sites provided there is sufficient anisotropy in the Lamb-Mössbauer recoilless fraction.