Nonnuclear Attractors in Heteronuclear Diatomic Systems.

Abstract

Nonnuclear attractors (NNAs) are observed in the electron density of a variety of systems, but the factors governing their appearance and their contribution to the system's properties remain a mystery. The NNA occurring in homo- and heteronuclear diatomics of main group elements with atomic numbers up to Z = 38 is investigated computationally (at the UCCSD/cc-pVQZ level of theory) by varying internuclear separations. This was done to determine the NNA occurrence window along with the evolution of the respective pseudoatomic basin properties. Two distinct categories of NNAs were detected in the data analyzed by means of catastrophe theory. Type "a" implies electronic charge transfer between atoms mediated by a pseudoatom. Type "b" shows an initial relocation of some electronic charge to a pseudoatom, which posteriorly returns to the same atom that donated this charge in the first place. A small difference of polarizability between the atoms that compose these heteronuclear diatomics seems to favor NNA formation. We also show that the NNA arising tends to result in some perceptible effects on molecular dipole and/or quadrupole moment curves against internuclear distance. Finally, successive cationic ionization results in the fast disappearance of the NNA in Li2 indicating that its formation is mainly governed by the field generated by the quantum mechanical electronic density and only depends parametrically on the bare nuclear field/potential at a given molecular geometry.