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Refined ab initio 6‐31G split‐valence basis set optimization of the molecular structures of biphenyl in twisted, planar, and perpendicular conformations
Author(s) -
Häfelinger Günter,
Regelmann Claus
Publication year - 1987
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.540080714
Subject(s) - dihedral angle , ab initio , planarity testing , chemistry , basis set , ab initio quantum chemistry methods , biphenyl , crystallography , molecular physics , intramolecular force , coupled cluster , energy minimization , computational chemistry , atomic physics , molecule , physics , density functional theory , stereochemistry , hydrogen bond , organic chemistry
Improved full ab initio optimizations of the molecular structure of biphenyl in twisted minimum energy, coplanar, and perpendicular conformations by use of Poles's GAUSSIAN 82 program have been performed in the 6‐31G basis set. These lead to geometries and energies of much higher reliability than our earlier STO‐3G results. The torsional angle Φ min obtained now is 45.41° in close agreement with the recent experimental value of 44.4° ± 1.2°. Calculated CC distances may be converted to experimental ED r g ‐values by means of independently determined linear regression correlations with very high statistical confidence, although they agree better with experimental x ray data for coplanar biphenyl without this correction. Calculated intramolecular angles are very similar for both STO‐3G and 6‐31G basis sets. The calculated torsional energy barrier towards Φ = 90° (Δ E 90 ) is 6.76 kJ/mol in close agreement with the experimental‐31G value of 6.5 ± 2.0 kJ/mol. For coplanar biphenyl with D 2h ‐symmetry the calculated torsional energy barrier Δ E 0 is 13.26 kJ/mol which is surprisingly much higher than the experimental value of 6.0 ± 2.1 kJ/mol. This discrepancy could not be resolved by optimizations assumed for two kinds of distortions of planarity of orthohydrogens from the molecular plane of the coplanar carbon atoms. But for the twisted minimum energy conformation asymmetric bending of ortho‐ H atoms lead to a torsional angle Φ min = 44.74° together with a dihedral angle towards ortho‐ H of 1.22°, and consequently even to an increase of torsional energy barriers to Δ E 0 = 13.51 and Δ E 90 = 6.91 kJ/mol.