A Stress Tensor and QTAIM Perspective on the Substituent Effects of Biphenyl Subjected to Torsion

作者：Jiajun, D.^*; Maza, J. R.; Xu, Y.; Xu, T.; Momen, R.; Kirk, S. R.; Jenkins, S.

来源：Journal of Computational Chemistry, 2016, 37(28): 2508-2517.

DOI：10.1002/jcc.24476

• Hammett constant
• biphenyl
• QTAIM
• stress tensor

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 phi, 0.0 degrees <= phi <= 180.0 degrees, of the C-C bond linking the two phenyl rings for C12H9-x, where x=N(CH3)(2), NH2, CH3, CHO, CN, NO2, on the entire molecule. QTAIM interpreted Hammett constants, a Delta H(r(b)) are introduced and constructed using the difference between the H(r(b)) value of C12H9-x and the C12H9-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, SO2NH2, SO2OH, COCl, CB3. Consistency is found for the QTAIM interpreted biphenyl substituent constants of the seven new groups y independently using the stress tensor polarizability P-sigma. In addition, a selection of future applications is discussed that highlight the usefulness of this approach.

• 出版日期2016-10-30
• 单位湖南师范大学