An electron-preceding perspective on the deformation of materials

Elements of Bader’s theory of atoms in molecules are combined with density-functional theory to provide an electron-preceding perspective on the deformation of materials. From this perspective, a network of atoms is changed by moving the bonds that connect them; the nuclei then follow. The electronic stress tensor is the key to understanding this process. Eigenvectors of the electronic stress tensor at critical points of the electron density provide insight into the “normal electronic modes” that accompany structural dynamics and rearrangements. Eigenvectors of the second-derivative matrix of the electron density emerge as effective approximations to the eigenvectors of the stress tensor; this makes it possible to apply our results to experimentally and computationally determined electron densities. To demonstrate the usefulness of our analysis, we show that (a) the low-frequency modes of ice Ic can be predicted from the eigenvectors of the second-derivative matrix and (b) the eigenvectors of the second-derivative matrix are associated with the direction of structural change during the pressure-induced phase transition from ice XI to a ferroelectric ice VIII-like structure. We conclude that the eigenvectors of the second-derivative matrix of the electron density are the key ingredient for constructing a dynamical theory of atoms in molecules.

An electron-preceding perspective on the deformation of materials Journal Articles