title: Parity nonconservation contribution to the nuclear magnetic resonance shielding constants of chiral molecules: a four-component relativistic study.
abstract: A systematic four-component relativistic study of the parity nonconservation (PNC) contribution to the (isotropic) NMR shielding constants of chiral molecules is presented for the P enantiomers of the series H(2)X(2) (X=(17)O,(33)S,(77)Se,(125)Te,(209)Po). The PNC contributions are obtained within a linear response approach at the Hartree-Fock level. A careful design of the basis sets is necessary. The four-component relativistic results based on the Dirac-Coulomb Hamiltonian are compared with the nonrelativistic Levy-Leblond results and those obtained by the spin-free modified Dirac Hamiltonian. The calculations confirm the nonrelativistic scaling law Z(2.4) of the PNC contribution with respect to nuclear charge Z. However, the calculations also show that the overall scaling is significantly modified by relativistic effects. The scalar relativistic effect scales as Z(4.7) for the selected set of molecules, whereas the spin-orbit effect, of opposite sign, scales better than Z(6) and completely dominates the PNC contribution for the heaviest elements. This opens up the intriguing possibility of the experimental observation of PNC effects on NMR parameters of molecules containing heavy atoms. The presented formalism is expected to be valuable in assisting the search for suitable candidate molecules.
authors.affiliation: Laboratoire de Chimie Quantique, Institut de Chimie de Strasbourg, LC3-UMR 7177 CNRS/Université Louis Pasteur, 4 Rue Blaise Pascal, F-67000 Strasbourg, France.
authors.forename: Radovan
authors.initials: R
authors.lastname: Bast
authors.forename: Peter
authors.initials: P
authors.lastname: Schwerdtfeger
authors.forename: Trond
authors.initials: T
authors.lastname: Saue