화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.112, No.23, 5187-5197, 2008
Radial exchange density and electron delocalization in molecules
The six-dimensional exchange density Gamma(X)(r(1),r(2)) is a measure of electron delocalization at the Hartree-Fock level. Fixation of r(1) to a constant point results in a three-dimensional function, which displays electron delocalization that originates from r(1) in position space. In this work, the dimensionality of Gamma(X)(r(1),r(2)) is lowered from six to four by integration with regard to r(2) over sphere surfaces of radius d, centered at r(1) = r. The resulting radial exchange density Gamma(X)(d,r) is visualized for constant d values as a function of r. This approach indicates regions of position space which are origins of delocalization over a certain distance d. The ' shape of these regions very strongly depends on d. Structures similar to pi orbital densities are observed at large d values (4.5 au) in unsaturated carbon compounds, while smaller values (1.5 au) can result in structures, which resemble the Laplacian of the electron density. The abundance of different spatial structures inherent in the radial exchange density implies interesting capabilities for the orbital-independent interpretation of electronic structures in position space.