Prototypical pi-pi dimers re-examined by means of high-level CCSDT(Q) composite ab inito methods

TL;DR

This study re-examines pi-pi stacking interactions in benzene-based dimers using high-level CCSDT(Q) methods, providing more accurate binding energies and insights into basis set convergence and post-CCSD(T) effects.

Contribution

It applies CCSDT(Q) composite ab initio methods to benzene dimers, offering improved accuracy over previous studies and analyzing the importance of post-CCSD(T) contributions.

Findings

Post-CCSD(T) contributions are destabilizing and significant for high-accuracy calculations.

Explicitly correlated calculations serve as a validation for conventional binding energies.

Basis set convergence behavior is clarified for various energy components.

Abstract

The benzene...ethene and parallel-displaced (PD) benzene...benzene dimers are the most fundamental systems involving p-p stacking interactions. Several high-level ab initio investigations calculated the binding energies of these dimers at the CCSD(T)/CBS level of theory using various approaches such as reduced virtual orbital spaces and/or MP2-based basis set corrections. Here we obtain CCSDT(Q) binding energies using a Weizmann-3-type approach. In particular, we extrapolate the SCF, CCSD, and (T) components using large heavy-atom augmented Gaussian basis sets (namely, SCF/jul-cc-pV{5,6}Z, CCSD/jul-cc-pV{Q,5}Z, and (T)/jul-cc-pV{T,Q}Z). We consider post-CCSD(T) contributions up to CCSDT(Q), inner-shell, scalar-relativistic, and Born-Oppenheimer corrections. Overall, our best relativistic, all-electron CCSDT(Q) binding energies are Delta Ee,all,rel = 1.234 (benzene...ethene) and 2.550 (benzene...benzene PD), Delta H0 = 0.949 (benzene...ethene) and 2.310 (benzene...benzene PD), and Delta H298 = 0.130 (benzene...ethene) and 1.461 (benzene...benzene PD) kcal/mol. Important conclusions are reached regarding the basis set convergence of the SCF, CCSD, (T), and post-CCSD(T) components. Explicitly correlated calculations are used as a sanity check on the conventional binding energies. Overall, post-CCSD(T) contributions are destabilizing by 0.028 (benzene...ethene) and 0.058(benzene...benzene) kcal/mol, thus they cannot be neglected if 0.1 kcal/mol accuracy is sought.