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Refined SMD Parameters for Bromine and Iodine Accurately Model Halogen‐Bonding Interactions in Solution
Author(s) -
Engelage Elric,
Schulz Nils,
Heinen Flemming,
Huber Stefan M.,
Truhlar Donald G.,
Cramer Christopher J.
Publication year - 2018
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.201803652
Subject(s) - parametrization (atmospheric modeling) , solvation , halogen , halogen bond , bromine , chemistry , hydrogen bond , ionic bonding , coulomb , implicit solvation , computational chemistry , thermodynamics , interpretation (philosophy) , acetonitrile , molecule , physics , quantum mechanics , organic chemistry , computer science , ion , alkyl , radiative transfer , electron , programming language
Motivated by the need to calculate liquid‐phase free energies of species and equilibria involving halogen bonding, recent experimental data were used to optimize new Coulomb radii for Br and I for use in the SMD universal solvation model for calculating free energies of solvation. The use of the SMD model with these parameters for Br and I and the SMD values of all other parameters is called SMD18. After parametrization, the SMD18 model was tested for data not used in the parametrization. These data are standard‐state free energies (equivalent to equilibrium constants) for 18 ionic equilibria involving Cl, Br, and I halogen bonding in acetonitrile, and the agreement of theory and experiment is satisfactory. The SMD18 model is then used to compare hydrogen bonding to halogen bonding and to reassess the interpretation of recent experiments.