On the local representation of the electronic momentum operator in atomic systems.
The local quantum theory is applied to the study of the momentum operator in atomic systems. Consequently, a quantum-based local momentum expression in terms of the single-electron density is determined. The limiting values of this function correctly obey two fundamental theorems: Kato's cusp condition and the Hoffmann-Ostenhof and Hoffmann-Ostenhof exponential decay. The local momentum also depicts the electron shell structure in atoms as given by its local maxima and inflection points. The integration of the electron density in a shell gives electron populations that are in agreement with the ones expected from the Periodic Table of the elements. The shell structure obtained is in agreement with the higher level of theory computations, which include the Kohn-Sham kinetic energy density. The average of the local kinetic energy associated with the local momentum is the Weizsacker kinetic energy. In conclusion, the local representation of the momentum operator provides relevant information about the electronic properties of the atom at any distance from the nucleus.
Bohórquez
Hugo J
HJ
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H 4J3, Canada. hugo.j.bohorquez@dal.ca
Boyd
Russell J
RJ