Collect. Czech. Chem. Commun. 1994, 59, 2567-2578

Electron Pairing and Chemical Bonds. Physical Meaning of Effective Pairs

Robert Ponec and Filip Uhlík

Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, 165 02 Prague 6-Suchdol, Czech Republic


The physical meaning of the so-called effective pairs which have been introduced recently within the formalism of pair population analysis is discussed using the analysis of conditional probabilities of electron density distribution for electron 1 with the reference electron fixed in a certain point 2. It is demonstrated that from the point of view of the mutual coupling of electron motions, the effective pairs behave analogously to singlet pairs. Based on this finding, effective pairs can be interpreted as the fraction of singlet pairs that is directly involved in bonding.