Description of halogen bonding in semiempirical quantum-mechanical and self-consistent charge density-functional tight-binding methods

This article analyzes the ability of semiempirical quantum-mechanical methods (PM6 and PM7) and self-consistent charge density-functional tight-binding (SCC-DFTB) method DFTB3 to describe halogen bonds. Calculations of the electrostatic potential on the surface of molecules containing halogens show that the σ-hole could be described well in modified neglect of diatomic overlap-based methods. The situation is more complex in the case of DFTB3 where a simpler model is used for the electrostatics, but short-ranged effects are covered in the Hamiltonian. All these methods can thus capture the effects that, for example, define the geometry of halogen bonds. The interaction energies are, however, affected by generally underestimated repulsion, which has been addressed earlier by standalone empirical corrections. Another approach to correcting this issue in DFTB3 is presented here-a modification of the energies of d-orbitals on halogens yields better results than the empirical correction in DFTB3-D3X, although it remains difficult to describe halogen and hydrogen bonds simultaneously. © 2019 Wiley Periodicals, Inc.