Relativistic four- and two-component calculations of parity violation effects in chiral tungsten molecules of the form NWXYZ (X, Y, Z = H, F, Cl, Br, or I).

Detlev Figgen (1) , Trond Saue (2) , Peter Schwerdtfeger (3)

1 Institut für Theoretische Chemie
2 Institut de Chimie de Strasbourg
3 CTCP - Centre for Theoretical Chemistry and Physics

Parity violation (PV) effects to the electronic ground state structure for a series of chiral tungsten molecules of the type NWXYZ (X, Y, Z = H, F, Cl, Br, or I) are compared using four- (Dirac) and two- (X2C) component relativistic Hartree-Fock and density functional theories. The results show the computationally more affordable two-component X2C approach yields accurate results for all molecules investigated. The PV energy differences between the two enantiomers range from as little as 0.4 Hz for NWClBrI to 140 Hz for NWHClI using a generalized gradient approximation including exact exchange (B3LYP). The W-N stretching mode in these molecules lies in the experimentally favorable CO(2) laser frequency range, and we therefore investigated PV effects in vibrational transitions using a single normal mode analysis. Here the PV frequency shift between the two enantiomers ranges from 1.6 mHz for NWFBrI to 710 mHz for NWHClI. Thus these types of molecules could be useful for the future detection of PV effects in chiral molecules.

Mots clés: chirality; density functional theory; Dirac equation; gas lasers; ground states; HF calculations; isomerism; parity; relativistic corrections; tungsten compounds; vibrational states

Domaines: Chimie théorique et/ou physique

Detlev Figgen, Trond Saue, Peter Schwerdtfeger. Relativistic four- and two-component calculations of parity violation effects in chiral tungsten molecules of the form NWXYZ (X, Y, Z = H, F, Cl, Br, or I).. Journal of Chemical Physics, 2010, 132 (23), pp.234310. ⟨10.1063/1.3439692⟩. ⟨hal-00760983⟩