Abstract: MATH/CHEM/COMP 2002, Dubrovnik, June 24-29, 2002

NATURE OF BONDING IN SF₆ AND CLi₆ FROM THE ANALYSIS OF DOMAIN AVERAGED FERMI HOLES

Robert  Ponec¹ and Xavier Girones²

¹Institute of Chemical Process Fundamentals, Czech Academy of Sciences, Prague 6-Suchdol, 165 02, Czech Republic

²Institute of Computational Chemistry, University of Girona, Campus Montilivi 17071, Girona, Catalonia, Spain  

The nature of bonding in SF₆ and CLi₆ was analysed using the recently proposed approach based on the scrutiny of the so-called domain averaged Fermi holes.  It has been shown that although the molecule of SF₆ does not satisfy the charge criterion of hypervalence, the actual picture of bonding is consistent with the traditional hypervalent model assuming the existence of six localized albeit very polar SF bonds around the central atom. On the other hand, while the molecule of CLi₆ represents the ideal candidate for hypervalence according to charge criterion, the picture of bonding is in this case considerably different from what the concept of hypervalence is traditionally associated with.