Estimates of electron correlation based on density expansions.

Abstract

Two methods for estimating the correlation energy of molecules and other electronic systems are discussed based on the assumption that the correlation energy can be partitioned between atomic regions. In the first method, the electron density is expanded in terms of atomic contributions using rigorous electron repulsion bounds, and in the second method, correlation contributions are associated with basis function pairs. These methods do not consider the detailed nature of localized excitations but instead define a correlation energy per electron factor that is unique to a specific atom. The correlation factors are basis function dependent and are determined by configuration interaction (CI) calculations on diatomic and hydride molecules. The correlation energy estimates are compared with the results of high-level CI calculations for a test set of 27 molecules representing a wide range of bonding environments (average error of 2.6%). An extension based on truncated CI calculations in which d-type and hydrogen p-type functions are eliminated from the virtual space combined with estimates of dynamical correlation contributions using atomic correlation factors is discussed and applied to the dissociation of several molecules.