Estimates of electron correlation based on density expansions

TL;DR

This paper introduces new methods for estimating molecular correlation energy by partitioning it into atomic regions using density expansions and basis function pairs, validated against high-level calculations.

Contribution

It presents novel density expansion techniques for correlation energy estimation, incorporating atomic contributions and basis function pairs, with validation against extensive molecular data.

Findings

Average error of 2.6% in correlation energy estimates

Effective extension for dissociation processes using truncated CI calculations

Correlation factors are basis function dependent and atom-specific

Abstract

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 one method, the electron density is expanded in terms of atomic contributions using rigorous electron repulsion bounds, and, in a second method, correlation contributions are associated with basis function pairs. The methods do not consider the detailed nature of localized excitations, but instead define a correlation energy per electron factor that that is unique to a specific atom. The correlation factors are basis function dependent and are determined by from configuration interaction calculations on diatomic and hydride molecules. The correlation energy estimates are compared with the results of high-level configuration interaction calculations for a test set of twenty-seven molecules representing a wide range of bonding environments (average error of 2.6%). An extension based on truncated CI calculations in which d- 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.