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Halogen−π Interactions between Benzene and X<sub>2</sub>/CX<sub>4</sub> (X = Cl, Br): Assessment of Various Density Functionals with Respect to CCSD(T)
Various
types of interactions between halogen (X) and π moiety
(X−π interaction) including halogen bonding play important
roles in forming the structures of biological, supramolecular, and
nanomaterial systems containing halogens and aromatic rings. Furthermore,
halogen molecules such as X<sub>2</sub> and CX<sub>4</sub> (X = Cl/Br)
can be intercalated in graphite and bilayer graphene for doping and
graphene functionalization/modification. Due to the X−π
interactions, though recently highly studied, their structures are
still hardly predictable. Here, using the coupled-cluster with single,
double, and noniterative triple excitations (CCSDÂ(T)), the Møller–Plesset
second-order perturbation theory (MP2), and various flavors of density
functional theory (DFT) methods, we study complexes of benzene (Bz)
with halogen-containing molecules X<sub>2</sub> and CX<sub>4</sub> (X = Cl/Br) and analyze various components of the interaction energy
using symmetry adapted perturbation theory (SAPT). As for the lowest
energy conformers (S1), X<sub>2</sub>–Bz is found to have the
T-shaped structure where the electropositive X atom-end of X<sub>2</sub> is pointing to the electronegative midpoint of CC bond of the Bz
ring, and CX<sub>4</sub>–Bz has the stacked structure. In addition
to this CX<sub>4</sub>–Bz (S1), other low energy conformers
of X<sub>2</sub>–Bz (S2/S3) and CX<sub>4</sub>–Bz (S2)
are stabilized primarily by the dispersion interaction, whereas the
electrostatic interaction is substantial. Most of the density functionals
show noticeable deviations from the CCSDÂ(T) complete basis set (CBS)
limit binding energies, especially in the case of strongly halogen-bonded
conformers of X<sub>2</sub>–Bz (S1), whereas the deviations
are relatively small for CX<sub>4</sub>–Bz where the dispersion
is more important. The halogen bond shows highly anisotropic electron
density around halogen atoms and the DFT results are very sensitive
to basis set. The unsatisfactory performance of many density functionals
could be mainly due to less accurate exchange. This is evidenced from
the good performance by the dispersion corrected hybrid and double
hybrid functionals. B2GP-PLYP-D3 and PBE0-TSÂ(Tkatchenko-Scheffler)/D3
are well suited to describe the X−π interactions adequately,
close to the CCSDÂ(T)/CBS binding energies (within ∼1 kJ/mol).
This understanding would be useful to study diverse X−π
interaction driven structures such as halogen containing compounds
intercalated between 2-dimensional layers