Relativistic effects in atomic and molecular properties

Abstract

Relativistic effects in atomic and molecular properties 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.