화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.110, No.29, 9273-9281, 2006
Spatial shape of electron delocalization: Structure of the laplacian of the negative exchange-correlation density
The Laplacian of the negative exchange-correlation density ( with respect to coordinate r(2)), del(2)(< r2 >)[-Gamma(sigma 1 sigma 2)(XC)(r(1), r(2))] =del X-2(< r2 >)sigma 1 sigma 2(r(1), r(2)), is proposed as an instrument for the analysis of electron delocalization in real space. It determines local concentrations in the amount of electrons that are delocalized from a reference point r(1) over space. Integration of the reference coordinate r(1) over an atomic basin Omega(n) gives the function del X-2(sigma 1 sigma 2)(Omega(n);r), which contains detailed information about the spatial shape of the delocalization that originates from an atom in a molecule. Its isosurface representations are richly structured and resemble molecular orbitals in their complexity and partly also in their shape. The sum over all del X-2(sigma 1 sigma 2)(Omega(n);r) functions of a molecule equals the Laplacian of the electron density del(2)rho(r), for which it provides a meaningful partitioning into atomic contributions.