The nature of the electronic interaction between congested hydrogens, like those in planar biphenyl, has been contested in recent years through the application of post-electronic structure bonding tools, e.g., QTAIM & IQA (the interaction is attractive) and NBO (the interaction is repulsive). We have reinvestigated this interaction from a third, perhaps more traditional, perspective that focuses on whether molecular structure and properties are better explained assuming an attractive or repulsive interaction. Molecular structures, vibrational spectra, and reaction energies were calculated for a series of molecules that QTAIM and IQA had previously identified as having bonding interactions between congested hydrogens. Our data reveal structural distortions, molecular vibrations, and reaction energies, that are more consistent with a repulsive hydrogen-hydrogen interaction in every case.

Curious case of Bader’s bond paths: A computational study of congested hydrogen-hydrogen interactions through the calculation of experimentally measurable parameters

251st National Meeting (2016)

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