Acta Phys. -Chim. Sin. ›› 2018, Vol. 34 ›› Issue (5): 503-513.doi: 10.3866/PKU.WHXB201709252

Special Issue: Special issue for Chemical Concepts from Density Functional Theory

• ARTICLE • Previous Articles     Next Articles

Revealing Molecular Electronic Structure via Analysis of Valence Electron Density

Tian LU*(),Qinxue CHEN   

  • Received:2017-08-31 Published:2018-01-24
  • Contact: Tian LU


Numerous real space functions have been purposed so far for unveiling chemically interesting molecular electronic structure characteristics, such as chemical bonds, lone pairs, and multicenter electronic conjugations. Among these analysis methods, electron localization function (ELF), Laplacian of electron density (∇2ρ), and deformation density (ρdef) were widely employed in practical research work. It is well known that the analysis of total molecular electron density is not sufficient for revealing much information about the molecular electronic structure like the above-mentioned methods. However, in this work, using several instances and by comparing with the ELF, ∇2ρ, and ρdef values, we show that it is possible to explore molecular electronic structure characteristics if one solely focuses on investigating the valence electron density distribution. It is found that for most cases, analysis of the very simple valence electron density conveys analogous information as ELF, ∇2ρ and ρdef analyses, with additional advantage of reduced computational complexity. We hope that this work will bring chemists' attention to the high importance of valence electron density, which has been largely ignored for a long time. It should also be noticed that the valence electron density analysis is not free from drawbacks, and when this method is unable to provide an informative picture, one has to use other analysis methods.

Key words: Electron density, Wavefunction analysis, Chemical bond, Electron localization Function, Atoms in molecules, Density functional theory, Laplacian of electron density, Deformation density