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

Elric Engelage, Nils Schulz, Flemming Heinen, Stefan M. Huber, Donald G Truhlar, Chris Cramer

Research output: Contribution to journalArticlepeer-review

24 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)15983-15987
Number of pages5
JournalChemistry - A European Journal
Volume24
Issue number60
DOIs
StatePublished - Oct 26 2018

Bibliographical note

Funding Information:
D.G.T. and C.J.C. acknowledge the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-17ER16362). E.E., N.S., F.H. and S.M.H. gratefully acknowledge funding by the Deutsche Forschungs-gemeinschaft (Cluster of Excellence RESOLV, EXC 1069). Computing resources were provided by the Minnesota Supercomputing Institute.

Funding Information:
D.G.T. and C.J.C. acknowledge the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-17ER16362). E.E., N.S., F.H. and S.M.H. gratefully acknowledge funding by the Deutsche Forschungsgemeinschaft (Cluster of Excellence RESOLV, EXC 1069). Computing resources were provided by the Minnesota Supercomputing Institute.

Keywords

  • halogen bonding
  • halogens
  • intrinsic solvation model
  • nitrogen heterocycles
  • supramolecular chemistry

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