title: Analysis of parity violation in chiral molecules.
abstract: In order to guide the experimental search for parity violation in molecular systems, in part motivated by the possible link to biomolecular homochirality, we present a detailed analysis in a relativistic framework of the mechanism behind the tiny energy difference between enantiomers induced by the weak force. A decomposition of the molecular expectation value into atomic contributions reveals that the effect can be thought of as arising from a specific mixing of valence s(1/2) and p(1/2) orbitals on a single center induced by a chiral molecular field. The intra-atomic nature of the effect is further illustrated by visualization of the electron chirality density and suggests that a simple model for parity violation in molecules may be constructed by combining pre-calculated atomic quantities with simple bonding models. A 2-component relativistic computational procedure is proposed which bridges the relativistic and non-relativistic approaches to the calculation of parity violation in chiral molecules and allows us to explore the single-center theorem in a variational setting.
authors.affiliation: Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway. radovan.bast@uit.no
authors.forename: Radovan
authors.initials: R
authors.lastname: Bast
authors.forename: Anton
authors.initials: A
authors.lastname: Koers
authors.forename: André Severo Pereira
authors.initials: AS
authors.lastname: Gomes
authors.forename: Miroslav
authors.initials: M
authors.lastname: Iliaš
authors.forename: Lucas
authors.initials: L
authors.lastname: Visscher
authors.forename: Peter
authors.initials: P
authors.lastname: Schwerdtfeger
authors.forename: Trond
authors.initials: T
authors.lastname: Saue
mesh_terms: D000596:Amino Acids / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D004583:Electrons; D008962:Models, Theoretical; D011789:Quantum Theory; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D000596:Amino Acids; D004247:DNA