ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Theoretical core effective potential methods are widely used in valence-only electron molecular calculations. These methods, which imply the frozen-core approximation, work well for the elements of the righthand side of the periodic table but are often unrealistic for metallic elements with highly polarizable cores. For these atoms one has to consider the polarization of the cores under the influence of the electric field created by the valence electrons. Moreover, relativistic corrections must be added for heavy atoms.Various theoretical approaches of core-valence interactions (polarization and core-valence correlations) will be reviewed, with a special emphasis on practical methods of calculation. The problem of handling the relativistic effects will mainly be discussed within the two-component Pauli formalism. It will be shown that the Foldy-Wouthuysen transformation is not the unique way for deriving relativistic corrections and that the second-order Dirac equation also provides a good starting point for obtaining relativistic corrections. Analytical exact results are given for the hydrogen atom. The accuracy of this approach is tested on many-electron atoms and molecules.It is finally shown that the problem of the core-valence separation is relevant to the general methodology of effective Hamiltonians that seems to provide the best promising way for filling the gap between the semiempirical and purely theoretical ab initio methods.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560290429
