Second-order scalar-relativistic Douglas-Kroll-Hess density functional calculations of the electric field gradient, including an analytic correction of the picture change error, were performed for 34 tin compounds of which molecular structures and 119Sn Mössbauer spectroscopy parameters are experimentally known. The components of the diagonalized electric field gradient tensor, Vxx, Vyy, Vzz, were used to determine the quantity V, which is proportional to the nuclear quadrupole splitting parameter ΔE. The slope of the linear correlation plot of the experimentally determined ΔE parameter versus the corresponding calculated V data allowed us to obtain an absolute value of the nuclear quadrupole moment Q of 119Sn equal to Q = 13.2 ±0.1 fm2. This is about 11% larger than the picture-change-error-affected value and in good agreement with previous estimates of the picture change error in compounds of similar atomic charge. Moreover, despite the variety of the tin compounds considered in this study, the new result is in excellent agreement with the previously determined most accurate value of Q for 119Sn of Q = 12.8 ±0.7 fm2, but with a noticeably narrower error bar. The reliability of the calibration method in the calculation of the ΔE parameter of tin compounds is within a margin of ±0,3 mm s-1 when compared to experimental data and does not depend on the inclusion of the picture change correction in the density functional calculations but is essentially determined by the use of an atomic natural orbital relativistic core-correlated basis set for the description of the core electron density. The results obtained suggest that the present picture-change-corrected Douglas-Kroll-Hess approach provides reliable electric field gradients in the case of closed-shell metal compounds involving elements up to the fifth row of the periodic table for which spin-orbit coupling is negligible.
|Number of pages||7|
|Journal||JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY|
|Publication status||Published - 2008|
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry