Suzuki Nayuta, Mitsuta Yuki, Okumura Mitsutaka, Yamanaka Shusuke
Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyoanaka, Osaka 560-0043, Japan.
Int J Mol Sci. 2016 Oct 25;17(11):1779. doi: 10.3390/ijms17111779.
We present the linear response function of bond-orders (LRF-BO) based on a real space integration scheme for molecular systems. As in the case of the LRF of density, the LRF-BO is defined as the response of the bond order of the molecule for the virtual perturbation. Our calculations show that the LRF-BO enables us not only to detect inductive and resonating effects of conjugating systems, but also to predict p values on substitution groups via linear relationships between the Hammett constants and the LRF-BO values for meta- and para-substituted benzoic acids. More importantly, the LRF-BO values for the O-H bonds strongly depend on the sites to which the virtual perturbation is applied, implying that the LRF-BO values include essential information about reaction mechanism of the acid-dissociation of substituted benzoic acids.
