title: Linear Response Function of Bond-Order.
abstract: 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 pKavalues 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.
authors: Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyoanaka, Osaka 560-0043, Japan. suzukin15@chem.sci.osaka-u.ac.jp.
authors: Nayuta
authors: N
authors: Suzuki
authors: Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyoanaka, Osaka 560-0043, Japan. mitsutay13@chem.sci.osaka-u.ac.jp.
authors: Yuki
authors: Y
authors: Mitsuta
authors: Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyoanaka, Osaka 560-0043, Japan. ok@chem.sci.osaka-u.ac.jp.
authors: Mitsutaka
authors: M
authors: Okumura
authors: Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyoanaka, Osaka 560-0043, Japan. syama@chem.sci.osaka-u.ac.jp.
authors: Shusuke
authors: S
authors: Yamanaka
mesh_terms: D001565:Benzoates / Q000737:chemistry*; D004583:Electrons; D007700:Kinetics; D008962:Models, Theoretical; D011789:Quantum Theory
chemical_list: D001565:Benzoates
keywords: acid dissociation reaction; bond order; linear response function