title: Quantitative Assessment of Halogen Bonding Utilizing Vibrational Spectroscopy.
abstract: A total of 202 halogen-bonded complexes have been studied using a dual-level approach: ωB97XD/aug-cc-pVTZ was used to determine geometries, natural bond order charges, charge transfer, dipole moments, electron and energy density distributions, vibrational frequencies, local stretching force constants, and relative bond strength orders n. The accuracy of these calculations was checked for a subset of complexes at the CCSD(T)/aug-cc-pVTZ level of theory. Apart from this, all binding energies were verified at the CCSD(T) level. A total of 10 different electronic effects have been identified that contribute to halogen bonding and explain the variation in its intrinsic strength. Strong halogen bonds are found for systems with three-center-four-electron (3c-4e) bonding such as chlorine donors in interaction with substituted phosphines. If halogen bonding is supported by hydrogen bonding, genuine 3c-4e bonding can be realized. Perfluorinated diiodobenzenes form relatively strong halogen bonds with alkylamines as they gain stability due to increased electrostatic interactions.
authors.affiliation: Computational and Theoretical Chemistry Group, Department of Chemistry, Southern Methodist University (SMU) , 3215 Daniel Avenue, Dallas, Texas 75275-0314, United States.
authors.forename: Vytor
authors.initials: V
authors.lastname: Oliveira
authors.affiliation: Computational and Theoretical Chemistry Group, Department of Chemistry, Southern Methodist University (SMU) , 3215 Daniel Avenue, Dallas, Texas 75275-0314, United States.
authors.forename: Elfi
authors.identifier: http://orcid.org/0000-0002-9658-5626
authors.initials: E
authors.lastname: Kraka
authors.affiliation: Computational and Theoretical Chemistry Group, Department of Chemistry, Southern Methodist University (SMU) , 3215 Daniel Avenue, Dallas, Texas 75275-0314, United States.
authors.forename: Dieter
authors.identifier: http://orcid.org/0000-0002-6213-5555
authors.initials: D
authors.lastname: Cremer