Electron Density Geometry and the Quantum Theory of Atoms in Molecules

01 December 2021, Version 4
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

A novel form of charge density analysis, that of isosurface curvature redistribution, is formulated and applied to the toy problem of carbonyl oxygen activation in formaldehyde. The isosurface representation of the electron charge density allows us to incorporate the rigorous geometric constraints of closed surfaces towards the analysis and chemical interpretation of the charge density response to perturbations. Visual inspection of 2D isosurface motion resulting from applied external electric fields reveals how isosurface curvature flows within and between atoms, and that a molecule can be uniquely and completely partitioned into chemically significant regions of positive and negative curvature. These concepts reveal that carbonyl oxygen activation proceeds primarily through curvature and charge redistribution within rather than between Bader atoms. Using gradient bundle analysis—the partitioning of formaldehyde into infinitesimal volume elements bounded by QTAIM zero flux surfaces—the observations from visual isosurface inspection are verified. The results of the formaldehyde carbonyl analysis are then shown to be transferable to the substrate carbonyl in the ketosteroid isomerase enzyme, laying the groundwork for extending this approach to the problems of enzymatic catalysis.

Keywords

QTAIM
GBA
electron density geometry
carbonyl activation

Supplementary materials

Title
Description
Actions
Title
Complete formaldehyde bader and gradient bundle integration data
Description
A set of comma-separated-values files containing the bader atom and gradient bundle integration data for the Formaldehyde analysis in the manuscript.
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.