Nuclear Quadrupole Moment of 119Sn
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- 作者：Giampaolo Barone ; Remigius Mastalerz ; Markus Reiher ; Roland Lindh
- 刊名：Journal of Physical Chemistry A
- 出版年：2008
- 出版时间：February 21, 2008
- 年：2008
- 卷：112
- 期：7
- 页码：1666 - 1672
- 全文大小：144K
- 年卷期：v.112,no.7(February 21, 2008)
- ISSN：1520-5215
文摘
Second-order scalar-relativistic Douglas-Kroll-Hess density functional calculations of the electric fieldgradient, including an analytic correction of the picture change error, were performed for 34 tin compoundsof which molecular structures and 119Sn Mössbauer spectroscopy parameters are experimentally known. Thecomponents of the diagonalized electric field gradient tensor, Vxx, Vyy, Vzz, were used to determine the quantityV, which is proportional to the nuclear quadrupole splitting parameter 
E. The slope of the linear correlationplot of the experimentally determined E parameter versus the corresponding calculated V data allowed usto obtain an absolute value of the nuclear quadrupole moment Q of 119Sn equal to Q = 13.2 ± 0.1 fm2. Thisis about 11% larger than the picture-change-error-affected value and in good agreement with previous estimatesof the picture change error in compounds of similar atomic charge. Moreover, despite the variety of the tincompounds considered in this study, the new result is in excellent agreement with the previously determinedmost accurate value of Q for 119Sn of Q = 12.8 ± 0.7 fm2, but with a noticeably narrower error bar. Thereliability of the calibration method in the calculation of the E parameter of tin compounds is within amargin of ±0.3 mm s-1 when compared to experimental data and does not depend on the inclusion of thepicture change correction in the density functional calculations but is essentially determined by the use of anatomic natural orbital relativistic core-correlated basis set for the description of the core electron density. Theresults obtained suggest that the present picture-change-corrected Douglas-Kroll-Hess approach providesreliable electric field gradients in the case of closed-shell metal compounds involving elements up to the fifthrow of the periodic table for which spin-orbit coupling is negligible.
E. The slope of the linear correlationplot of the experimentally determined E parameter versus the corresponding calculated V data allowed usto obtain an absolute value of the nuclear quadrupole moment Q of 119Sn equal to Q = 13.2 ± 0.1 fm2. Thisis about 11% larger than the picture-change-error-affected value and in good agreement with previous estimatesof the picture change error in compounds of similar atomic charge. Moreover, despite the variety of the tincompounds considered in this study, the new result is in excellent agreement with the previously determinedmost accurate value of Q for 119Sn of Q = 12.8 ± 0.7 fm2, but with a noticeably narrower error bar. Thereliability of the calibration method in the calculation of the E parameter of tin compounds is within amargin of ±0.3 mm s-1 when compared to experimental data and does not depend on the inclusion of thepicture change correction in the density functional calculations but is essentially determined by the use of anatomic natural orbital relativistic core-correlated basis set for the description of the core electron density. Theresults obtained suggest that the present picture-change-corrected Douglas-Kroll-Hess approach providesreliable electric field gradients in the case of closed-shell metal compounds involving elements up to the fifthrow of the periodic table for which spin-orbit coupling is negligible.