Exploring Intrinsic Bond Properties with the Fukui Matrix from Conceptual Density Matrix Functional Theory

• DOI: 10.1021/acs.jctc.4c01627
• Publication Date: 2025-02-04T06:51:41Z
• Authors: Bin Wang; Paul Geerlings; Farnaz Heidar-Zadeh; Paul W. Ayers; Frank De Proft
• Keywords: Matrix (chemical analysis)

We extend the traditional conceptual density functional theory (CDFT) to matrix (CDMFT) by replacing external potential v(r) one-electron integral hrs in energy functional. This approach provides a new path for investigating intrinsic bond properties such as reactivity. The derivation of Fukui matrix, i.e., derivative P with respect number electrons N, is elucidated, and result illustrated case study on H2O. shown play crucial role quantifying changes strength electron removal or addition processes via order (∂B∂N)−. Using Mayer different atoms-in-molecules partitioning methods, we show that first-order response quantity, agrees well finite difference changes. (bond function) reactivity descriptor. demonstrate this predicting regioselectivity classical electrophilic reaction (the bromination alkenes) initial electron-driven cleavage mass spectrometry. Specifically, captures all major signals from experimental spectra series small molecules variety groups.