Refined SMD Parameters for Bromine and Iodine Accurately Model Halogen-Bonding Interactions in Solution
Abstract
Abstract 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.
- Authors:
-
[1];
[1];
[2];
[2]
- Ruhr-Univ., Bochum (Germany). Organische Chemie I, Fakultät für Chemie und Biochemie
- Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst., Dept. of Chemistry, Chemical Theory Center
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1495024
- Alternate Identifier(s):
- OSTI ID: 1476941
- Grant/Contract Number:
- SC0008688; FG02-17ER16362
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 24; Journal Issue: 60; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; halogen bonding; halogens; intrinsic solvation model; nitrogen heterocycles; supramolecular chemistry
Citation Formats
Engelage, Elric, Schulz, Nils, Heinen, Flemming, Huber, Stefan M., Truhlar, Donald G., and Cramer, Christopher J. Refined SMD Parameters for Bromine and Iodine Accurately Model Halogen-Bonding Interactions in Solution. United States: N. p., 2018.
Web. doi:10.1002/chem.201803652.
Engelage, Elric, Schulz, Nils, Heinen, Flemming, Huber, Stefan M., Truhlar, Donald G., & Cramer, Christopher J. Refined SMD Parameters for Bromine and Iodine Accurately Model Halogen-Bonding Interactions in Solution. United States. https://doi.org/10.1002/chem.201803652
Engelage, Elric, Schulz, Nils, Heinen, Flemming, Huber, Stefan M., Truhlar, Donald G., and Cramer, Christopher J. Tue .
"Refined SMD Parameters for Bromine and Iodine Accurately Model Halogen-Bonding Interactions in Solution". United States. https://doi.org/10.1002/chem.201803652. https://www.osti.gov/servlets/purl/1495024.
@article{osti_1495024,
title = {Refined SMD Parameters for Bromine and Iodine Accurately Model Halogen-Bonding Interactions in Solution},
author = {Engelage, Elric and Schulz, Nils and Heinen, Flemming and Huber, Stefan M. and Truhlar, Donald G. and Cramer, Christopher J.},
abstractNote = {Abstract 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.},
doi = {10.1002/chem.201803652},
journal = {Chemistry - A European Journal},
number = 60,
volume = 24,
place = {United States},
year = {Tue Oct 09 00:00:00 EDT 2018},
month = {Tue Oct 09 00:00:00 EDT 2018}
}
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Scheme 1: Halide complexation by iodoimidazolium salts.
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