title: A stress tensor and QTAIM perspective on the substituent effects of biphenyl subjected to torsion.
abstract: The Quantum Theory of Atoms in Molecules (QTAIM) defines quantities in 3D space that can be easily obtained from routine quantum chemical calculations. The present investigation shows that local properties can be related quantitatively to measures traditionally connected to experimental data, such as Hammett constants. We consider the specific case of substituted biphenyl to quantify the effects of a torsion φ, 0.0° ≤ φ ≤ 180.0°, of the C-C bond linking the two phenyl rings for C12 H9 -x, where x = N(CH3 )2 , NH2 , CH3 , CHO, CN, NO2, on the entire molecule. QTAIM interpreted Hammett constants, aΔH(rb ) are introduced and constructed using the difference between the H(rb ) value of C12 H9 -x and the C12 H9 -H, biphenyl which is the reference molecule, with a constant of proportionality a. This investigation unexpectedly yields very good or good agreement for the x groups with the Hammett para-, meta-, and ortho-substituent constants and is checked against para-substituted benzene. We then proceed to present the interpreted substituent constants of seven new biphenyl substituent groups, where tabulated Hammett substituent constant values are not available; y = SiH3 , ZnCl, COOCH3 , SO2 NH2 , SO2 OH, COCl, CB3 . Consistency is found for the QTAIM interpreted biphenyl substituent constants of the seven new groups y independently using the stress tensor polarizability Pσ . In addition, a selection of future applications is discussed that highlight the usefulness of this approach. © 2016 Wiley Periodicals, Inc.
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha Hunan, 410081, China.
authors.forename: D
authors.initials: D
authors.lastname: Jiajun
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha Hunan, 410081, China.
authors.forename: J R
authors.initials: JR
authors.lastname: Maza
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha Hunan, 410081, China.
authors.forename: Y
authors.initials: Y
authors.lastname: Xu
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha Hunan, 410081, China.
authors.forename: T
authors.initials: T
authors.lastname: Xu
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha Hunan, 410081, China.
authors.forename: R
authors.initials: R
authors.lastname: Momen
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha Hunan, 410081, China.
authors.forename: S R
authors.initials: SR
authors.lastname: Kirk
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province of MOE, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha Hunan, 410081, China.
authors.forename: S
authors.identifier: 0000-0002-4288-7653
authors.initials: S
authors.lastname: Jenkins
keywords: Hammett constant; QTAIM; biphenyl; stress tensor