TWOE Code: An Efficient Tool for Explicit Partition of Coupled Cluster and Configuration Interaction Energies into Atomic and Diatomic Contributions

The efficient implementation of the TWOE program for evaluating the atomic and interatomic energy components at post-HF level was developed. The systematic convergence of these terms up to a near full-CI limit was performed for the first time for a series of coupled cluster methods: CCSD -> CCSDT -> CCSDTQ -> CCSDTQP. A comparison with corresponding CI approaches (up to fifth excitation level) is additionally discussed. For a set of diatomic systems, it was demonstrated that, along with a full molecular energy convergence, all its components are also converged but with different patterns. It was found that not all components are decreased in their values at increasing computational rank. For instance, atomic energy parts are decreased while interatomic (interaction) energies are increased as the limiting level is approached. Two schemes were employed for atomic partition of molecules: the Baders approach and planes dissection. Influence of dynamical correlation effects on atomic energy components was analyzed in detail. Current TWOE implementation allows one, in principle, to work with any ab initio method providing the two-particle density matrix. It is believed that the developed program will be a useful tool for a real space energy decomposition that helps to reveal the most peculiar points in the structure of the total and correlation energies of a molecule.

Automated summary

The efficient implementation of the TWOE program for evaluating atomic and interatomic energy components at post-HF level is discussed, with a systematic convergence of terms for various coupled cluster methods and comparison with CI approaches. It is found that not all components decrease in value as computational rank increases, with different patterns for atomic and interatomic energy convergence observed. The program allows for working with any ab initio method providing the two-particle density matrix, and is believed to be a useful tool for energy decomposition in real space.