Universität zu Köln

Ciupka, J., Hanrath, M. and Dolg, M. (2011). Localization scheme for relativistic spinors. J. Chem. Phys., 135 (24). MELVILLE: AMER INST PHYSICS. ISSN 1089-7690

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Abstract

A new method to determine localized complex-valued one-electron functions in the occupied space is presented. The approach allows the calculation of localized orbitals regardless of their structure and of the entries in the spinor coefficient matrix, i.e., one-, two-, and four-component Kramers-restricted or unrestricted one-electron functions with real or complex expansion coefficients. The method is applicable to localization schemes that maximize (or minimize) a functional of the occupied spinors and that use a localization operator for which a matrix representation is available. The approach relies on the approximate joint diagonalization (AJD) of several Hermitian (symmetric) matrices which is utilized in electronic signal processing. The use of AJD in this approach has the advantage that it allows a reformulation of the localization criterion on an iterative 2 x 2 pair rotating basis in an analytical closed form which has not yet been described in the literature for multi-component (complex-valued) spinors. For the one-component case, the approach delivers the same Foster-Boys or Pipek-Mezey localized orbitals that one obtains from standard quantum chemical software, whereas in the multicomponent case complex-valued spinors satisfying the selected localization criterion are obtained. These localized spinors allow the formulation of local correlation methods in a multi-component relativistic framework, which was not yet available. As an example, several heavy and super-heavy element systems are calculated using a Kramers-restricted self-consistent field and relativistic two-component pseudopotentials in order to investigate the effect of spin-orbit coupling on localization. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3670415]

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Ciupka, J. UNSPECIFIED UNSPECIFIED UNSPECIFIED Hanrath, M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Dolg, M. UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-483257
DOI:	10.1063/1.3670415
Journal or Publication Title:	J. Chem. Phys.
Volume:	135
Number:	24
Date:	2011
Publisher:	AMER INST PHYSICS
Place of Publication:	MELVILLE
ISSN:	1089-7690
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language ENERGY-CONSISTENT PSEUDOPOTENTIALS; CORRELATED MOLECULAR CALCULATIONS; EFFECTIVE CORE POTENTIALS; GAUSSIAN-BASIS SETS; AB-INITIO; TIME-REVERSAL; UNITARY; OPTIMIZATION; ALGORITHMS; SYMMETRY Multiple languages Chemistry, Physical; Physics, Atomic, Molecular & Chemical Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/48325