Partitioning dynamic electron correlation energy: Viewing Møller-Plesset correlation energies through Interacting Quantum Atom (IQA) energy partitioning
Abstract
Here MP2, MP3 and MP4(SDQ) are energy-partitioned for the first time within the Interacting Quantum Atoms (IQA) context, as proof-of-concept for H2, He2 and HF. Energies are decomposed into four primary energy contributions: (i) atomic self-energies, and atomic interaction energies comprising of (ii) Coulomb, (iii) exchange and (iv) dynamic election correlation terms. We generate and partition one- and two-particle density-matrices to obtain all atomic energy components. This work suggests that, in terms of Van der Waals dispersion, the correlation energies represent an atomic stabilisation, by proximity to other atoms, as opposed to direct interactions with other nearby atoms.
- Publication:
-
Chemical Physics Letters
- Pub Date:
- October 2016
- DOI:
- 10.1016/j.cplett.2016.09.019
- Bibcode:
- 2016CPL...662..228M