EXPECTATION VALUES OF OPERATORS IN APPROXIMATE 2-COMPONENT RELATIVISTIC THEORIES

Citation
M. Barysz et Aj. Sadlej, EXPECTATION VALUES OF OPERATORS IN APPROXIMATE 2-COMPONENT RELATIVISTIC THEORIES, Theoretical chemistry accounts, 97(1-4), 1997, pp. 260-270
Citations number
66
Categorie Soggetti
Chemistry Physical
ISSN journal
1432881X
Volume
97
Issue
1-4
Year of publication
1997
Pages
260 - 270
Database
ISI
SICI code
1432-881X(1997)97:1-4<260:EVOOIA>2.0.ZU;2-H
Abstract
Two methods for the evaluation of expectation values with approximate two-component relativistic functions are analysed. The first of them i s based oil the change of picture for the operator whose expectation v alue is to be calculated and associated with approximations leading to the given two-component relativistic wave fnnction. This method, thou gh hardly used in numerical calculations, gives the expectation values that directly reflect the accuracy of the wave function used for thei r calculation. The second method, most commonly used in calculations, neglects the picture change and is shown always to introduce an error of the order of alpha(2), where alpha is the fine structure constant. This error is present independently of the accuracy of the approximate two-component wave function. The perturbation formalism developed ill this paper is illustrated by calculations of relativistic corrections to the expectation values of r(-1) for arbitrary states of hydrogenic ions.