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Intermolecular Interactions of Large Systems: Boron Nitrides, Acenes, and Coronenes

Vladimir Fishman, Jan M. L. Martin, A. Daniel Boese

TL;DR

This work extends a non-covalent benchmark to larger systems by including borazine dimers and coronene/acene geometries, enabling an analysis of how interaction energies scale with system size. It combines DFT geometry optimization with a broad set of high-level wavefunction methods and SAPT analyses to dissect dispersion, induction, and electrostatic contributions across diverse species and geometries. The study finds near-linear scaling of correlation energies per subunit in multiple series, provides best-estimate slopes toward the CBS limit using CCSD(T) and higher-order corrections, and delivers concrete coronene dimer energy estimates that illuminate the behavior of large π-systems. Together, these results offer practical guidance for benchmarking non-covalent interactions in large complexes and clarify the relative roles of different interaction components as system size grows.

Abstract

In a recent contribution [Fishman, V.; Lesiuk, M.; Martin, J.M.L.; Boese, A.D., J. Chem. Theory Comput. 2025, 21, 2311-2324], we introduced another angle at benchmarking non-covalent interactions by not just benchmarking interaction energies of different species, but by considering the evolution of interaction energies with increasing system size. Here, we extend the benchmark set to more species, such as electrostatically bound borazine dimers as well as the minima structures of parallel displaced acene and coronene dimers. While the minimum structures of the parallel displaced acene dimers yield similar results to previously published sandwich-structured acenes, the borazine dimers behave vastly different, yielding yet a more complete picture on non-covalent interactions and their scalability. In contrast, the polycyclic aromatic hydrocarbon structures -- coronenes sandwich-stacked and coronenes parallel displaced -- give results consistent with those obtained for both types of the polyacene series, resulting in an updated estimate for the coronene dimer energy.

Intermolecular Interactions of Large Systems: Boron Nitrides, Acenes, and Coronenes

TL;DR

This work extends a non-covalent benchmark to larger systems by including borazine dimers and coronene/acene geometries, enabling an analysis of how interaction energies scale with system size. It combines DFT geometry optimization with a broad set of high-level wavefunction methods and SAPT analyses to dissect dispersion, induction, and electrostatic contributions across diverse species and geometries. The study finds near-linear scaling of correlation energies per subunit in multiple series, provides best-estimate slopes toward the CBS limit using CCSD(T) and higher-order corrections, and delivers concrete coronene dimer energy estimates that illuminate the behavior of large π-systems. Together, these results offer practical guidance for benchmarking non-covalent interactions in large complexes and clarify the relative roles of different interaction components as system size grows.

Abstract

In a recent contribution [Fishman, V.; Lesiuk, M.; Martin, J.M.L.; Boese, A.D., J. Chem. Theory Comput. 2025, 21, 2311-2324], we introduced another angle at benchmarking non-covalent interactions by not just benchmarking interaction energies of different species, but by considering the evolution of interaction energies with increasing system size. Here, we extend the benchmark set to more species, such as electrostatically bound borazine dimers as well as the minima structures of parallel displaced acene and coronene dimers. While the minimum structures of the parallel displaced acene dimers yield similar results to previously published sandwich-structured acenes, the borazine dimers behave vastly different, yielding yet a more complete picture on non-covalent interactions and their scalability. In contrast, the polycyclic aromatic hydrocarbon structures -- coronenes sandwich-stacked and coronenes parallel displaced -- give results consistent with those obtained for both types of the polyacene series, resulting in an updated estimate for the coronene dimer energy.
Paper Structure (10 sections, 7 equations, 4 figures, 4 tables)

This paper contains 10 sections, 7 equations, 4 figures, 4 tables.

Table of Contents

  1. Introduction
  2. Computational Details
  3. Strong Correlation Diagnostics
  4. Different species investigated
  5. Basis Set Effects
  6. Local Correlation
  7. Electronic Structure Methods
  8. Best Estimates of Slopes
  9. Coronene Dimer
  10. Conclusions

Figures (4)

  • Figure 1: Correlation energies in kJ/mol vs. number of rings using the cc-pV$n$Z and aug-cc-pV$n$Z ($n$=D-5) basis sets at the LNO-CCSD(T) level with Tight threshold including MP2 corrections.
  • Figure 2: Correlation energies (kJ/mol) derived from various coupled cluster methods in as a function of system size per number of rings.
  • Figure 3: Correlation energies derived from various post-Hartree-Fock (and DFT) methods in kJ/mol vs. number of rings.
  • Figure 4: Deviations of Correlation energies from reference CCSD(T) method in kJ/mol vs. number of subunits.