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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
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Cited by: 11 works
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Figures / Tables:

Scheme 1 Scheme 1: Halide complexation by iodoimidazolium salts.

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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

Use of Solution-Phase Vibrational Frequencies in Continuum Models for the Free Energy of Solvation
journal, December 2011

  • Ribeiro, Raphael F.; Marenich, Aleksandr V.; Cramer, Christopher J.
  • The Journal of Physical Chemistry B, Vol. 115, Issue 49
  • DOI: 10.1021/jp205508z

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide
journal, January 2007

  • Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 2
  • DOI: 10.1021/jp065403l

The Halogen Bond
journal, January 2016


Organocatalysis by Neutral Multidentate Halogen-Bond Donors
journal, May 2013

  • Kniep, Florian; Jungbauer, Stefan H.; Zhang, Qi
  • Angewandte Chemie International Edition, Vol. 52, Issue 27
  • DOI: 10.1002/anie.201301351

Iod(III)-Verbindungen als Halogenbrückenkatalysatoren
journal, March 2018

  • Heinen, Flemming; Engelage, Elric; Dreger, Alexander
  • Angewandte Chemie, Vol. 130, Issue 14
  • DOI: 10.1002/ange.201713012

Counterion influence on the N–I–N halogen bond
journal, January 2015

  • Bedin, Michele; Karim, Alavi; Reitti, Marcus
  • Chemical Science, Vol. 6, Issue 7
  • DOI: 10.1039/C5SC01053E

Free-Energy Surfaces for Liquid-Phase Reactions and Their Use To Study the Border Between Concerted and Nonconcerted α,β-Elimination Reactions of Esters and Thioesters
journal, August 2010

  • Kim, Yongho; Mohrig, Jerry R.; Truhlar, Donald G.
  • Journal of the American Chemical Society, Vol. 132, Issue 32
  • DOI: 10.1021/ja101104q

Principles and Applications of Halogen Bonding in Medicinal Chemistry and Chemical Biology
journal, January 2013

  • Wilcken, Rainer; Zimmermann, Markus O.; Lange, Andreas
  • Journal of Medicinal Chemistry, Vol. 56, Issue 4
  • DOI: 10.1021/jm3012068

Property-optimized Gaussian basis sets for molecular response calculations
journal, October 2010

  • Rappoport, Dmitrij; Furche, Filipp
  • The Journal of Chemical Physics, Vol. 133, Issue 13
  • DOI: 10.1063/1.3484283

Combining metals with halogen bonds
journal, January 2008

  • Brammer, Lee; Mínguez Espallargas, Guillermo; Libri, Stefano
  • CrystEngComm, Vol. 10, Issue 12
  • DOI: 10.1039/b812927d

Isothermal Calorimetric Titrations on Charge-Assisted Halogen Bonds: Role of Entropy, Counterions, Solvent, and Temperature
journal, May 2012

  • Walter, Sebastian M.; Kniep, Florian; Rout, Laxmidhar
  • Journal of the American Chemical Society, Vol. 134, Issue 20
  • DOI: 10.1021/ja2119207

Supramolecular Binding Thermodynamics by Dispersion-Corrected Density Functional Theory
journal, July 2012


Halogen Bonding in Supramolecular Chemistry
journal, July 2015

  • Gilday, Lydia C.; Robinson, Sean W.; Barendt, Timothy A.
  • Chemical Reviews, Vol. 115, Issue 15
  • DOI: 10.1021/cr500674c

Assessing the Accuracy and Performance of Implicit Solvent Models for Drug Molecules: Conformational Ensemble Approaches
journal, May 2013

  • Kolář, Michal; Fanfrlík, Jindřich; Lepšík, Martin
  • The Journal of Physical Chemistry B, Vol. 117, Issue 19
  • DOI: 10.1021/jp402117c

General parameterized SCF model for free energies of solvation in aqueous solution
journal, October 1991

  • Cramer, Christopher J.; Truhlar, Donald G.
  • Journal of the American Chemical Society, Vol. 113, Issue 22
  • DOI: 10.1021/ja00022a017

Halogen Bonds: Benchmarks and Theoretical Analysis
journal, March 2013

  • Kozuch, Sebastian; Martin, Jan M. L.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 4
  • DOI: 10.1021/ct301064t

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

Consistent van der Waals Radii for the Whole Main Group
journal, May 2009

  • Mantina, Manjeera; Chamberlin, Adam C.; Valero, Rosendo
  • The Journal of Physical Chemistry A, Vol. 113, Issue 19
  • DOI: 10.1021/jp8111556

Halogen bonding in solution: thermodynamics and applications
journal, January 2013

  • Beale, Thomas M.; Chudzinski, Michael G.; Sarwar, Mohammed G.
  • Chem. Soc. Rev., Vol. 42, Issue 4
  • DOI: 10.1039/C2CS35213C

A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions
journal, January 2017

  • Goerigk, Lars; Hansen, Andreas; Bauer, Christoph
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 48
  • DOI: 10.1039/C7CP04913G

Halogen bonded supramolecular complexes and networks
journal, January 2008


A DFT assessment of some physical properties of iodine-centered halogen bonding and other non-covalent interactions in some experimentally reported crystal geometries
journal, January 2018

  • Varadwaj, Arpita; Varadwaj, Pradeep R.; Marques, Helder M.
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 22
  • DOI: 10.1039/C8CP01085D

Electrochemical activation of a tetrathiafulvalene halogen bond donor in solution
journal, January 2016

  • Oliveira, R.; Groni, S.; Fave, C.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 23
  • DOI: 10.1039/C6CP02219G

The Interaction Modes of Haloimidazolium Salts in Solution
journal, December 2017

  • Schulz, Nils; Sokkar, Pandian; Engelage, Elric
  • Chemistry - A European Journal, Vol. 24, Issue 14
  • DOI: 10.1002/chem.201705032

Iodine(III) Derivatives as Halogen Bonding Organocatalysts
journal, March 2018

  • Heinen, Flemming; Engelage, Elric; Dreger, Alexander
  • Angewandte Chemie International Edition, Vol. 57, Issue 14
  • DOI: 10.1002/anie.201713012

Halogen Bonding in Organic Synthesis and Organocatalysis
journal, July 2016

  • Bulfield, David; Huber, Stefan M.
  • Chemistry - A European Journal, Vol. 22, Issue 41
  • DOI: 10.1002/chem.201601844

Halogen bonding in metal–organic–supramolecular networks
journal, March 2010

  • Bertani, Roberta; Sgarbossa, Paolo; Venzo, Alfonso
  • Coordination Chemistry Reviews, Vol. 254, Issue 5-6
  • DOI: 10.1016/j.ccr.2009.09.035

Organokatalyse mit neutralen mehrzähnigen Halogenbrückendonoren
journal, May 2013

  • Kniep, Florian; Jungbauer, Stefan H.; Zhang, Qi
  • Angewandte Chemie, Vol. 125, Issue 27
  • DOI: 10.1002/ange.201301351

Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
journal, August 2006

  • Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 32
  • DOI: 10.1021/jp063552y

Activation of Michael Acceptors by Halogen-Bond Donors
journal, December 2017


Halogen bonded supramolecular capsules: a challenging test case for quantum chemical methods
journal, January 2016

  • Sure, Rebecca; Grimme, Stefan
  • Chemical Communications, Vol. 52, Issue 64
  • DOI: 10.1039/C6CC03664C

Calculating Free Energy Changes in Continuum Solvation Models
journal, February 2016


Halogen Bonding from Dispersion-Corrected Density-Functional Theory: The Role of Delocalization Error
journal, November 2014

  • Otero-de-la-Roza, A.; Johnson, Erin R.; DiLabio, Gino A.
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 12
  • DOI: 10.1021/ct500899h

Thermodynamics of Halogen Bonding in Solution: Substituent, Structural, and Solvent Effects
journal, February 2010

  • Sarwar, Mohammed G.; Dragisic, Bojan; Salsberg, Lee J.
  • Journal of the American Chemical Society, Vol. 132, Issue 5
  • DOI: 10.1021/ja9086352

The intramolecular hydrogen bonded–halogen bond: a new strategy for preorganization and enhanced binding
journal, January 2018

  • Riel, Asia Marie S.; Decato, Daniel A.; Sun, Jiyu
  • Chemical Science, Vol. 9, Issue 26
  • DOI: 10.1039/C8SC01973H

Self-Consistent Reaction Field Model for Aqueous and Nonaqueous Solutions Based on Accurate Polarized Partial Charges
journal, October 2007

  • Marenich, Aleksandr V.; Olson, Ryan M.; Kelly, Casey P.
  • Journal of Chemical Theory and Computation, Vol. 3, Issue 6
  • DOI: 10.1021/ct7001418

Development and assessment of new exchange-correlation functionals
journal, October 1998

  • Hamprecht, Fred A.; Cohen, Aron J.; Tozer, David J.
  • The Journal of Chemical Physics, Vol. 109, Issue 15
  • DOI: 10.1063/1.477267

Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008

  • Chai, Jeng-Da; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 44
  • DOI: 10.1039/b810189b

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    A halogen-bonding-catalysed Nazarov cyclisation reaction
    journal, January 2019

    • Dreger, Alexander; Wonner, Patrick; Engelage, Elric
    • Chemical Communications, Vol. 55, Issue 57
    • DOI: 10.1039/c9cc02816a

    Effects of dynamic pedal motion and static disorder on thermal expansion within halogen-bonded co-crystals
    journal, January 2019

    • Juneja, Navkiran; Unruh, Daniel K.; Bosch, Eric
    • New Journal of Chemistry, Vol. 43, Issue 47
    • DOI: 10.1039/c9nj04833b

    A halogen-bonding-catalysed Nazarov cyclisation reaction
    journal, January 2019

    • Dreger, Alexander; Wonner, Patrick; Engelage, Elric
    • Chemical Communications, Vol. 55, Issue 57
    • DOI: 10.1039/c9cc02816a

    Effects of dynamic pedal motion and static disorder on thermal expansion within halogen-bonded co-crystals
    journal, January 2019

    • Juneja, Navkiran; Unruh, Daniel K.; Bosch, Eric
    • New Journal of Chemistry, Vol. 43, Issue 47
    • DOI: 10.1039/c9nj04833b

    “Anti‐Electrostatic” Halogen Bonding
    journal, April 2020

    • Holthoff, Jana M.; Engelage, Elric; Weiss, Robert
    • Angewandte Chemie International Edition
    • DOI: 10.1002/anie.202003083

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