Dirac‐exact relativistic methods: the normalized elimination of the small component method1. (12th February 2014)

• Record Type: Journal Article
• Authors: Cremer, Dieter; Zou, Wenli; Filatov, Michael
• Is Part Of: Wiley interdisciplinary reviews. Volume 4:Number 5(2014:Sep./Oct.)
• Page Start: 436
• Page End: 467
• Publication Date: 2014-02-12
• Subjects: Chemistry, Physical and theoretical -- Periodicals; Cheminformatics -- Periodicals; Biochemistry -- Periodicals; 541.220285
• DOI: 10.1002/wcms.1181
• Languages: English
• ISSNs: 1759-0876

Abstract

<abstract abstract-type="main" id="wcms1181-abs-0001"> <title> <x xml:space="preserve">Abstract</x> </title> <p id="wcms1181-para-0001">Dirac‐exact relativistic methods, i.e., 2‐ or 1‐component methods which exactly reproduce the one‐electron energies of the original 4‐component Dirac method, have established a standard for reliable relativistic quantum chemical calculations targeting medium‐ and large‐sized molecules. Their development was initiated and facilitated in the late 1990s by Dyall's development of the normalized elimination of the small component (NESC). Dyall's work has fostered the conversion of NESC and related (later developed) methods into routinely used, multipurpose Dirac‐exact methods by which energies, first‐order, and second‐order properties can be calculated at computational costs, which are only slightly higher than those of nonrelativistic methods. This review summarizes the development of a generally applicable 1‐component NESC algorithm leading to the calculation of reliable energies, geometries, electron density distributions, electric moments, electric field gradients, hyperfine structure constants, contact densities and Mössbauer isomer shifts, nuclear quadrupole coupling constants, vibrational frequencies, infrared intensities, and static electric dipole polarizabilities. In addition, the derivation and computational possibilities of 2‐component NESC methods are discussed and their use for the calculation of spin‐orbit coupling (SOC) effects in connection with spin‐orbit splittings and SOC‐corrected energies are demonstrated. The impact of scalar relativistic and spin‐orbit effects on molecular properties is presented. <italic>WIREs Comput Mol Sci</italic> 2014, 4:436–467.</p> <p id="wcms1181-para-0004">Conflict of interest: The authors have declared no conflicts of interest for this article.</p> <p>For further resources related to this article, please visit the <ext-link ext-link-type="uri" xlink:href="http://wires.wiley.com/remdoi.cgi?doi=10.1002/wcms.1181" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">WIREs website</ext-link>.</p> </abstract>