skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Refined SMD Parameters for Bromine and Iodine Accurately Model Halogen-Bonding Interactions in Solution

Abstract

Motivated by the need to calculate liquid-phase free energies of species and equilibria involving halogen bonding, we used recent experimental data 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 involve Cl, Br, and I halogen bonding in acetonitile, 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:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Ruhr-Univ., Bochum (Germany). Organische Chemie I, Fakultät für Chemie und Biochemie
  2. 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) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
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. doi: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. doi: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 = {Motivated by the need to calculate liquid-phase free energies of species and equilibria involving halogen bonding, we used recent experimental data 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 involve Cl, Br, and I halogen bonding in acetonitile, 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 = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
  • DOI: 10.1021/jp810292n

van der Waals Volumes and Radii
journal, March 1964

  • Bondi, A.
  • The Journal of Physical Chemistry, Vol. 68, Issue 3, p. 441-451
  • DOI: 10.1021/j100785a001