acta physica slovaca

Acta Physica Slovaca 60, No.3, 259-391 (2010) (132 pages)


Miroslav Iliaš1, Vladimír Kellö2, Miroslav Urban 2,3
    1Department of Chemistry, Faculty of Natural Sciences, Matej Bel University, Banská Bystrica, Slovakia
    2Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Bratislava, Slovakia
    3Slovak University of Technology in Bratislava, Faculty of Materials Science and Technology, Trnava, Slovakia

Full text: ::pdf :: (Received 17 May 2010, accepted 1 June 2010)

Abstract: We present an overview of basic principles and methods of the relativistic quantum chemistry. Practical aspects of different methods will be discussed stressing their capability of providing accurate predictions of molecular properties, particularly in species containing a heavy metal element. We will present a series of examples showing the importance of relativistic effects in a variety of molecular properties including electron affinities, ionization potentials, reaction and dissociation energies, electric, spectroscopic and other properties. It is possible to recognize a link between these properties and behaviour of materials in some cases. Particular attention is paid to relativistic calculations of the nuclear quadrupole moments for which accurate theoretical electric field gradient is combined with data from the microwave spectra. Important aspect of the present paper is understanding of trends in electronically related atoms throughout the Mendeleev Periodic Table rather than focusing on highly accurate numbers. We will show that relativistic effects represent an unavoidable instrument for explaining some unexpected properties of heavy metal containing compounds. We will also discuss an interplay between the many–electron correlation and relativistic effects.

DOI: 10.2478/v10155-010-0003-1

PACS: 31.15.A-, 31.15.aj, 31.15.ap,, 31.15.V-, 31.30.jc,, 32.10.Hq
Keywords: Relativistic effects, Electron correlation, Change of picture, Ionization potentials, Electron affinities, Excitation energies, Dipole moments and polarizabilities, Electric field gradients, Nuclear quadrupole moments, Multiple bonds, Intermolecular interactions, NMR.
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