Nonexistance of hydrogen-hydrogen bonding in planar biphenyl and the failure of Atoms-In-Molecules (AIM) theory

ORGN 39

Jordi Poater, j.poater@few.vu.nl1, Miquel Solà, miquel.sola@udg.es2, and A. Patrícia Bento, ap.bento@few.vu.nl1. (1) Department of Theoretical Chemistry, Vrije Universiteit Amsterdam, De Boelelaan 1083, NL-1081 HV Amsterdam, Netherlands, (2) Departament de Quimica and Institut de Quimica Computacional, Universitat de Girona, Campus de Montilivi, 17071 Girona, Spain
In this talk we show that there is H–H steric repulsion, no H–H bonding between ortho-hydrogen atoms in planar biphenyl (see illustration) as follows from our quantitative phenyl–phenyl bond energy decomposition and numerical experiments carried out using Kohn-Sham DFT. This and other evidence falsifies the hypothesis that AIM theory's "bond paths" and "bond critical points" are sufficient indicators for bonding interactions.

 

Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High-Energy Species
8:00 AM-11:40 AM, Sunday, 10 September 2006 Moscone Center -- Room 133, Oral

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006