Electron Density Geometry and the Quantum Theory of Atoms in Molecules
datasetposted on 15.12.2021, 07:43 by Timothy R. Wilson, Anastassia N. Alexandrova, M. E. Eberhart
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 toward 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 the 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 curvatures. These concepts reveal that carbonyl oxygen activation proceeds primarily through curvature and charge redistribution within rather than between Bader atoms. Using gradient bundle analysisthe partitioning of formaldehyde into infinitesimal volume elements bounded by QTAIM zero-flux surfacesthe 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.
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rigorous geometric constraintsketosteroid isomerase enzymeflux surfaces electron density geometryclosed surfaces towardchemically significant regionscharge density responsecarbonyl oxygen activationcharge density analysisvisual isosurface inspectionisosurface curvature redistributionformaldehyde carbonyl analysisvisual inspectionsubstrate carbonylisosurface representationtoy problemquantum theoryqtaim zeronovel formnegative curvaturesenzymatic catalysisconcepts revealcompletely partitionedchemical interpretation