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Hydrogen–hydrogen interaction in planar biphenyl: A theoretical study based on the interacting quantum atoms and H irshfeld atomic energy partitioning methods
Author(s) -
Eskandari Kiamars,
Van Alsenoy Christian
Publication year - 2014
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23698
Subject(s) - atoms in molecules , chemistry , steric effects , atomic physics , molecule , biphenyl , interaction energy , planar , hydrogen , van der waals radius , crystallography , computational chemistry , chemical physics , van der waals force , physics , stereochemistry , computer graphics (images) , organic chemistry , computer science
The nature of H‐H interaction between ortho ‐hydrogen atoms in planar biphenyl is investigated by two different atomic energy partitioning methods, namely fractional occupation iterative Hirshfeld (FOHI) and interacting quantum atoms (IQA), and compared with the traditional virial‐based approach of quantum theory of atoms in molecules (QTAIM). In agreement with Bader's hypothesis of HH bonding, partitioning the atomic energy into intra‐atomic and interatomic terms reveals that there is a net attractive interaction between the ortho ‐hydrogens in the planar biphenyl. This falsifies the classical view of steric repulsion between the hydrogens. In addition, in contrast to the traditional QTAIM energy analysis, both FOHI and IQA show that the total atomic energy of the ortho ‐hydrogens remains almost constant when they participate in the H‐H interaction. Although, the interatomic part of atomic energy of the hydrogens plays a stabilizing role during the formation of the HH bond, it is almost compensated by the destabilizing effects of the intra‐atomic parts and consequently, the total energy of the hydrogens remains constant. The trends in the changes of intra‐atomic and interatomic energy terms of ortho ‐hydrogens during HH bond formation are very similar to those observed for the H 2 molecule. © 2014 Wiley Periodicals, Inc.