On the electron leak problem in orbital-free embedding calculations

Abstract

Computer simulation methods using orbital level of description only for a selected part of the larger systems are prone to the artificial charge leak to the parts which are described without orbitals. The absence of orbitals in one of the subsystems makes it impossible to impose explicitly the orthogonality condition. Using the subsystem formulation of density functional theory, it is shown that the absence of explicit condition of orthogonality between orbitals belonging to different subsystems, does not cause any breakdown of this type of description for the chosen intermolecular complexes (F- H2 O and Li+ H2 O), for which a significant charge-leak problem could be a priori expected. © 2006 American Institute of Physics.