Open AccessPerspective: Chemical Information Encoded in Electron Density.
Author(s) -
Julia ContrerasGarcía,
Weitao Yang
Publication year - 2018
Publication title -
hal (le centre pour la communication scientifique directe)
Language(s) - Uncategorized
Resource type - Journals
pISSN - 1000-6818
DOI - 10.3866/pku.whxb201801261
Subject(s) - delocalized electron , spins , statistical physics , simple (philosophy) , topology (electrical circuits) , atoms in molecules , perspective (graphical) , electron , density functional theory , computer science , physics , computational chemistry , chemistry , theoretical physics , chemical physics , quantum mechanics , mathematics , condensed matter physics , artificial intelligence , philosophy , epistemology , combinatorics
In this perspective, we review the chemical information encoded in electron density and other ingredients used in semilocal functionals. This information is usually looked at from the functional point of view: the exchange density or the enhancement factor are discussed in terms of the reduced density gradient. However, what parts of a molecule do these 3D functions represent? We look at these quantities in real space, aiming to understand the electronic structure information they encode and provide an insight from the quantum chemical topology (QCT). Generalized gradient approximations (GGAs) provide information about the presence of chemical interactions, whereas meta-GGAs can differentiate between the different bonding types. By merging these two techniques, we show new insight into the failures of semilocal functionals owing to three main errors: fractional charges, fractional spins, and non-covalent interactions. We build on simple models. We also analyze the delocalization error in hydrogen chains, showing the ability of QCT to reveal the delocalization error introduced by semilocal functionals. Then, we show how the analysis of localization can help understand the fractional spin error in alkali atoms, and how it can be used to correct it. Finally, we show that the poor description of GGAs of isodesmic reactions in alkanes is due to 1,3-interactions.