A Minimum Quantum Chemistry CCSD(T)/CBS Data Set of Dimeric Interaction Energies for Small Organic Functional Groups: Heterodimers.

Abstract

We extend our previous quantum chemistry calculations of interaction energies for 31 homodimers of small organic functional groups (the SOFG-31 data set) by including 239 heterodimers with monomers selected within the SOFG-31 data set, thus resulting in the SOFG-31+239 data set. The minimum-level theoretical scheme contains (1) the basis set superposition error corrected supermolecule (BSSE-SM) approach for intermolecular interactions; (2) the second-order Møller–Plesset perturbation theory (MP2) with the Dunning’s aug-cc-pVXZ (X = D, T, Q) basis sets for the geometry optimization and correlation energy calculations; and (3) the single-point energy calculations with the coupled cluster with single, double, and perturbative triple excitations method at the complete basis set limit [CCSD(T)/CBS] using the well-tested extrapolation methods for the MP2 energy calibrations. In addition, we have performed a parallel series of energy decomposition calculations based on the symmetry adapted perturbation theory (SAPT) in order to gain chemical insights. That the above procedure cannot be further reduced has been proven to be very crucial for constructing reliable data sets of interaction energies. The calculated CCSD(T)/CBS interaction energy data can serve as a benchmark for testing or training less accurate but more efficient calculation methods, such as the electronic density functional theory. As an application, we employ a segmental SAPT model previously developed for the SOFG-31 data set to predict binding energies of large heterodimer complexes. These model energy “quanta” can be used in coarse-grained molecular dynamics simulations by avoiding large-scale calculations.