Premium
Theoretical Insights into the Nature of Halogen Bonding in Prereactive Complexes
Author(s) -
Hill J. Grant,
Hu Xiaojun
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201204312
Subject(s) - ionic bonding , halogen , halogen bond , electrostatics , chemical physics , chemistry , cluster (spacecraft) , dispersion (optics) , charge (physics) , computational chemistry , atomic physics , molecular physics , crystallography , physics , ion , computer science , organic chemistry , quantum mechanics , alkyl , programming language
Benchmark quality geometries and interaction energies for the prereactive halogen‐bonded complexes of dihalogens and ammonia, including hypothetical astatine containing dihalogens, have been produced via explicitly correlated coupled cluster methods. The application of local electron correlation partitioning reveals dispersion, electrostatics and ionic substitutions all contribute significantly to the interaction energy, with a linear relationship between the ionic substitutions and the degree of charge transfer. Potential energy curves for H 3 N⋅⋅⋅ClF show that as the relative orientations of the two subunits are manipulated appreciable interactions can be found at considerably angular displaced geometries, signifying lower directionality in halogen bonding than previously supposed.