A Comparison of the Interacting Quantum Atoms (IQA) Analysis of the Two‐Particle Density‐Matrices of MP4SDQ and CCSD

Abstract

Within the quantum topological energy partitioning method called Interacting Quantum Atoms (IQA) we transition from Møller‐Plesset (MP4SDQ) to CCSD in calculating intra‐ and interatomic electron correlation energies for a set of hydrides, diatomics, a few simple molecules and non‐covalently bonded complexes, using the uncontracted basis set 6‐31++G(2d,2p). CCSD‐IQA allows a more rigorous analysis of atomic electron correlation than that offered by Møller‐Plesset, which returns IQA contributions that are identical to Hartree–Fock counterparts except for two‐electron terms. The CCSD‐IQA analysis returns bond and other interatomic correlation energies that are typically much larger in magnitude than the MP4SDQ values. Crisp patterns of energy transferability are detected in water clusters, both for intra‐atomic and interatomic correlation energies. CCSD determines that the intra‐atomic correlation energy of an oxygen drops by 15 kJ·mol–1 for donating a hydrogen and by 25 kJ·mol–1 for accepting a hydrogen.