Virial relations in density embedding

Abstract

AbstractThe accuracy of charge‐transfer excitation energies, solvatochromic shifts, and other environmental effects calculated via various density‐embedding techniques depend critically on the approximations employed for the nonadditive noninteracting kinetic energy functional, . Approximating this functional remains an important challenge in electronic‐structure theory. To assist in the development and testing of approximations for , we derive two virial relations for fragments in molecules. These establish separate connections between the nonadditive kinetic energies of the noninteracting and interacting systems of electrons, and quantities such as the electron‐nuclear attraction forces, the partition (or embedding) energy and potential, and the Kohn‐Sham potentials of the system and its parts. We numerically verify both relations on diatomic molecules.