Electron density
Can chemical bonding and reactivity be understood and predicted? The electron density can, in principle, describe all molecular properties and various functionals of the electron density have been proposed as tools for this purpose, including the Laplacian of the electron density and the electron localization function.
|
|
|
Current work
The electron density is the fundamental variable in our approach to the quantum-classical correspondence. Purely quantum terms are expressed as functionals of the electron density. With Ricardo Mosna, Universidade Estadual de Campinas, Brazil and Luigi Delle Site, Max Planck Institute for Polymer Research, Germany, our goal is to extend and generalize our approach to
- Strengthen the relevance of our work to the connection between quantum mechanics and Information Theory.
- Strengthen the relevance of our work to the construction of orbital-free kinetic-energy functionals.
- Understand and predict chemical bonding and reactivity using the one-electron potential and other functionals of the electron density.
Recent work
- We have explored formal aspects of the electron density (with Ricardo Mosna, Universidade Estadual de Campinas, Brazil and Luigi Delle Site, Max Planck Institute for Polymer Research, Germany). We proposed an approach to the quantum-classical correspondence based on deformations of the momentum and kinetic operators of quantum mechanics. We constructed classical versions of momentum and kinetic operators which, in addition to the standard quantum expressions, contain terms that are functionals of the electron density. In our approach the kinetic energy is decomposed as the sum of a classical term and a purely quantum term which is essentially identical to the Fisher information.
- For a series of amines we examined the correspondence between the one-electron potential and the Laplacian of the electron density as indicators of proton affinity (with Wai-To Chan, PDF). Proton affinities for a series of amines and phosphines are shown to exhibit linear correlation with valence minima of N and P.
- For a variety of diatomics we examined valence shell structures in the distributions of the one-electron potential and the Laplacian of the electron density (with Wai-To Chan, PDF). We proposed an alternative definition of the valence shell charge concentration as the outermost region for which the one-electron potential is negative.
