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Nuclear quadrupole moment of Sn-119

Barone, Giampaolo; Mastalerz, Remigius; Reiher, Markus and Lindh, Roland LU (2008) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 112(7). p.1666-1672
Abstract
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 Sn-119 Mossbauer spectroscopy parameters are experimentally known. The components of the diagonalized electric field gradient tensor, V-xx,V-yy, V-zz, were used to determine the quantity V, which is proportional to the nuclear quadrupole splitting parameter Delta E. The slope of the linear correlation plot of the experimentally determined Delta E parameter versus the corresponding calculated V data allowed us to obtain an absolute value of the nuclear quadrupole moment Q of Sn-119 equal to Q =... (More)
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 Sn-119 Mossbauer spectroscopy parameters are experimentally known. The components of the diagonalized electric field gradient tensor, V-xx,V-yy, V-zz, were used to determine the quantity V, which is proportional to the nuclear quadrupole splitting parameter Delta E. The slope of the linear correlation plot of the experimentally determined Delta E parameter versus the corresponding calculated V data allowed us to obtain an absolute value of the nuclear quadrupole moment Q of Sn-119 equal to Q = 13.2 +/- 0.1 fm(2). 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 Sn-119 of Q = 12.8 +/- 0.7 fm(2), but with a noticeably narrower error bar. The reliability of the calibration method in the calculation of the Delta E 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. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
112
issue
7
pages
1666 - 1672
publisher
The American Chemical Society
external identifiers
  • wos:000253222100037
  • scopus:39849102507
ISSN
1520-5215
DOI
10.1021/jp710388t
language
English
LU publication?
yes
id
26c737f1-c0cf-4e3a-b44b-3752e5fb334d (old id 1196467)
date added to LUP
2008-09-10 11:24:38
date last changed
2017-05-21 04:07:56
@article{26c737f1-c0cf-4e3a-b44b-3752e5fb334d,
  abstract     = {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 Sn-119 Mossbauer spectroscopy parameters are experimentally known. The components of the diagonalized electric field gradient tensor, V-xx,V-yy, V-zz, were used to determine the quantity V, which is proportional to the nuclear quadrupole splitting parameter Delta E. The slope of the linear correlation plot of the experimentally determined Delta E parameter versus the corresponding calculated V data allowed us to obtain an absolute value of the nuclear quadrupole moment Q of Sn-119 equal to Q = 13.2 +/- 0.1 fm(2). 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 Sn-119 of Q = 12.8 +/- 0.7 fm(2), but with a noticeably narrower error bar. The reliability of the calibration method in the calculation of the Delta E 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.},
  author       = {Barone, Giampaolo and Mastalerz, Remigius and Reiher, Markus and Lindh, Roland},
  issn         = {1520-5215},
  language     = {eng},
  number       = {7},
  pages        = {1666--1672},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Nuclear quadrupole moment of Sn-119},
  url          = {http://dx.doi.org/10.1021/jp710388t},
  volume       = {112},
  year         = {2008},
}