Method of evaluating chemical shifts of X-ray emission lines in molecules and solids

Abstract

Method of evaluating chemical shifts of X-ray emission lines for sufficiently heavy atoms (beginning from period 4 elements) in chemical compounds is developed. This method is based on the pseudopotential model and one-center restoration method (to reconstruct the proper electronic structure in heavy-atom cores). The approximations of instantaneous transition and frozen inner core spinors of the atom are used for derivation of an expression for chemical shift as a difference between mean values of some effective operator. The method allows one to avoid evaluating small values (chemical shifts ~$0.01-1$ eV) as differences of very large values (transition energies ~ $1-100$ keV in various compounds). The results of our calculations of chemical shifts for the $K{\alpha }_1$, $K{\alpha }_2$, and L transitions of the group 14 metal cations with respect to neutral atoms are presented. The calculations of chemical shift of $K{\alpha }_1$-line in the Pb-core transition within PbO and PbF${}_2$ with respect to the neutral Pb are also performed and discussed. The accuracy of the used approximations is discussed and quality of the performed calculations is analyzed.

14 pages, 8 tables, PHYSICAL REVIEW A 88, 062511 (2013)

References in corpus (2)

• Configuration interaction calculation of hyperfine and P,T-odd constants on ^{207}PbO excited states for the electron EDM experiments
• Two-step method for precise calculation of core properties in molecules

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