15min:
RIGOROUS RELATIVISTIC METHODS FOR ADDRESSING \calP- AND \calT-NONCONSERVATION IN HEAVY-ELEMENT MOLECULES.

TIMO FLEIG, Laboratoire de Chimie et Physique Quantiques, Université Paul Sabatier Toulouse 3, Toulouse, France.

A new and rigorous method for accurate ab-initio calculations of the electron electric dipole moment \calP,T-odd interaction constant is presented. The approach uses string-based Configuration Interaction wavefunctions\footnote\beginminipage[t]15.0cm S.~Knecht, H.~J.~Å.~Jensen and T.~Fleig J.~Chem.~Phys. \underline\textbf132, 014108 (2010)
T.~Fleig, H.~J.~Å.~Jensen, J.~Olsen and L.~Visscher J.~Chem.~Phys. \underline\textbf124, 104106 (2006) \endminipage and Dirac four-component spinors as one-particle basis functions, and the \calP,T-odd constant is obtained as an expectation value over these correlated wavefunctions. The method has been applied to the HfF+ molecular ion to determine spectroscopic constants for four low-lying electronic states. For one of these states ( Omega = 1) we have determined a new accurate benchmark value for the effective electric field E eff correlating 34 valence and outer atomic core electrons and using wavefunction expansions with nearly 5 cdot 108 coefficients. For the Omega = 1 state of the ThO molecule the first ab-initio result for the electron EDM interaction constant is presented.

Aspects of modern all-electron relativistic many-body approaches applicable to both atoms and molecules will be discussed, including perspectives for the treatment of other interesting candidate systems and \calP- or \calP,T-non-conserving effects in molecular systems.