Topology of electron-electron interactions in atoms and molecules. II. The correlation cage

摘要: The concept of the correlation cage provides new insights into electron–electron interactions in atoms and molecules. constitutes domain space interelectron distance vectors R within which effects are substantial. Its shape size entirely determined by topological properties electron intracule density I(R), thus avoiding any references to ill-defined “uncorrelated” quantities. Integration observables related I(R) over affords quantitative measures correlation. number strongly correlated pairs Mcorr[I], their repulsion energy Wcorr[I], volume Vcorr[I] that characterizes spatial extent functionals I(R). ratio κ[I] I(0)Vcorr[I] strength short-range effects, is small for systems such as H− closer one those with weaker effects.