Quantifying the Impact of Halogenation on Intermolecular Interactions and Binding Modes of Aromatic Molecules

Halogenation of aromatic molecules is frequently used to modulate intermolecular interactions with ramifications for optoelectronic and mechanical properties. In this work, we accurately quantify and understand the nature of intermolecular interactions in perhalogenated benzene (PHB) clusters. Using benchmark binding energies from the fixed-node diffusion Monte Carlo (FN-DMC) method, we show that generalized Kohn–Sham semicanonical projected random phase approximation (GKS-spRPA) plus approximate exchange kernel (AKX) provides reliable interaction energies with mean absolute error (MAE) of 0.23 kcal/mol. Using the GKS-spRPA+AXK method, we quantify the interaction energies of several binding modes of PHB clusters ((C₆X₆)_n; X = F, Cl, Br, I; n = 2, 3). For a given binding mode, the interaction energies increase 3–4 times from X = F to X = I; the X–X binding modes have energies in the range of 2–4 kcal/mol, while the π–π binding mode has interaction energies in the range of 4–12 kcal/mol. SAPT-DFT-based energy decomposition analysis is then used to show that the equilibrium geometries are dictated primarily by the dispersion and exchange interactions. Finally, we test the accuracy of several dispersion-corrected density functional approximations and show that only the r2SCAN-D4 method has a low MAE and correct long-range behavior, which makes it suitable for large-scale simulations and for developing structure–function relationships of halogenated aromatic systems.