Electron Density Geometry and the Quantum Theory of Atoms in Molecules

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.

Electron Density Geometry and the Quantum Theory of Atoms in Molecules

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.

Electron Density Geometry and the Quantum Theory of Atoms in Molecules

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.

$$\alpha $$-Dirac-harmonic maps from closed surfaces

Abstract$$\alpha $$ α -Dirac-harmonic maps are variations of Dirac-harmonic maps, analogous to $$\alpha $$ α -harmonic maps that were introduced by Sacks–Uhlenbeck to attack the existence problem for harmonic maps from closed surfaces. For $$\alpha >1$$ α > 1 , the latter are known to satisfy a Palais–Smale condition, and so, the technique of Sacks–Uhlenbeck consists in constructing $$\alpha $$ α -harmonic maps for $$\alpha >1$$ α > 1 and then letting $$\alpha \rightarrow 1$$ α → 1 . The extension of this scheme to Dirac-harmonic maps meets with several difficulties, and in this paper, we start attacking those. We first prove the existence of nontrivial perturbed $$\alpha $$ α -Dirac-harmonic maps when the target manifold has nonpositive curvature. The regularity theorem then shows that they are actually smooth if the perturbation function is smooth. By $$\varepsilon $$ ε -regularity and suitable perturbations, we can then show that such a sequence of perturbed $$\alpha $$ α -Dirac-harmonic maps converges to a smooth coupled $$\alpha $$ α -Dirac-harmonic map.

Existence of (Dirac-)harmonic Maps from Degenerating (Spin) Surfaces

We study the existence of harmonic maps and Dirac-harmonic maps from degenerating surfaces to a nonpositive curved manifold via the scheme of Sacks and Uhlenbeck. By choosing a suitable sequence of $$\alpha $$ α -(Dirac-)harmonic maps from a sequence of suitable closed surfaces degenerating to a hyperbolic surface, we get the convergence and a cleaner energy identity under the uniformly bounded energy assumption. In this energy identity, there is no energy loss near the punctures. As an application, we obtain an existence result about (Dirac-)harmonic maps from degenerating (spin) surfaces. If the energies of the map parts also stay away from zero, which is a necessary condition, both the limiting harmonic map and Dirac-harmonic map are nontrivial.

Self-shaping liquid crystal droplets by balancing bulk elasticity and interfacial tension

The shape diversity and controlled reconfigurability of closed surfaces and filamentous structures, universally found in cellular colonies and living tissues, are challenging to reproduce. Here, we demonstrate a method for the self-shaping of liquid crystal (LC) droplets into anisotropic and three-dimensional superstructures, such as LC fibers, LC helices, and differently shaped LC vesicles. The method is based on two surfactants: one dissolved in the LC dispersed phase and the other in the aqueous continuous phase. We use thermal stimuli to tune the bulk LC elasticity and interfacial energy, thereby transforming an emulsion of polydispersed, spherical nematic droplets into numerous, uniform-diameter fibers with multiple branches and vice versa. Furthermore, when the nematic LC is cooled to the smectic-A LC phase, we produce monodispersed microdroplets with a tunable diameter dictated by the cooling rate. Utilizing this temperature-controlled self-shaping of LCs, we demonstrate life-like smectic LC vesicle structures analogous to the biomembranes in living systems. Our experimental findings are supported by a theoretical model of equilibrium interface shapes. The shape transformation is induced by negative interfacial energy, which promotes a spontaneous increase of the interfacial area at a fixed LC volume. The method was successfully applied to many different LC materials and phases, demonstrating a universal mechanism for shape transformation in complex fluids.

Stable approximations for axisymmetric Willmore flow for closed and open surfaces

For a hypersurface in $\mathbb R^3$, Willmore flow is defined as the $L^2$--gradient flow of the classical Willmore energy: the integral of the squared mean curvature. This geometric evolution law is of interest in differential geometry, image reconstruction and mathematical biology. In this paper, we propose novel numerical approximations for the Willmore flow of axisymmetric hypersurfaces. For the semidiscrete continuous-in-time variants we prove a stability result. We consider both closed surfaces, and surfaces with a boundary. In the latter case, we carefully derive weak formulations of suitable boundary conditions. Furthermore, we consider many generalizations of the classical Willmore energy, particularly those that play a role in the study of biomembranes. In the generalized models we include spontaneous curvature and area difference elasticity (ADE) effects, Gaussian curvature and line energy contributions. Several numerical experiments demonstrate the efficiency and robustness of our developed numerical methods.