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Updated: Aug 11, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Dispersion Energy from the Time-Independent Coupled-Cluster Polarization Propagator
Piotr S Żuchowski1, Robert Moszynski2
1Faculty of Physics, Astronomy and Applied Informatics, Institute of Physics, Nicolas Copernicus University in Torun, Grudziadzka 5/7, Torun87-100, Poland.
Abstract:
We present a new method of calculation of the dispersion energy in the second-order symmetry-adapted perturbation theory. Using the Longuet-Higgins integral and time-independent coupled-cluster response theory, one shows that the general expression for the dispersion energy can be written in terms of cluster amplitudes and the excitation operators σ, which can be obtained by solving a linear equation. We introduced an approximate scheme dubbed CCPP2(T) for the dispersion energy accurate to the second order of intramonomer correlation, which includes certain classes to be summed to infinity. Assessment of the accuracy of the CCPP2(T) dispersion energy against the FCI dispersion for He2 demonstrates its high accuracy. For more complex systems, CCPP2(T) matches the accuracy of the best methods introduced for calculations of dispersion so far. The method can be extended to higher-order levels of excitations, providing a systematically improvable theory of dispersion interaction.
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