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Modeling Organochlorine Compounds and the σ-Hole Effect Using a Polarizable Multipole Force Field
[Image: see text] The charge distribution of halogen atoms on organochlorine compounds can be highly anisotropic and even display a so-called σ-hole, which leads to strong halogen bonds with electron donors. In this paper, we have systematically investigated a series of chloromethanes with one to fo...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2014
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4065202/ https://www.ncbi.nlm.nih.gov/pubmed/24484473 http://dx.doi.org/10.1021/jp411671a |
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author | Mu, Xiaojiao Wang, Qiantao Wang, Lee-Ping Fried, Stephen D. Piquemal, Jean-Philip Dalby, Kevin N. Ren, Pengyu |
author_facet | Mu, Xiaojiao Wang, Qiantao Wang, Lee-Ping Fried, Stephen D. Piquemal, Jean-Philip Dalby, Kevin N. Ren, Pengyu |
author_sort | Mu, Xiaojiao |
collection | PubMed |
description | [Image: see text] The charge distribution of halogen atoms on organochlorine compounds can be highly anisotropic and even display a so-called σ-hole, which leads to strong halogen bonds with electron donors. In this paper, we have systematically investigated a series of chloromethanes with one to four chloro substituents using a polarizable multipole-based molecular mechanics model. The atomic multipoles accurately reproduced the ab initio electrostatic potential around chloromethanes, including CCl(4), which has a prominent σ-hole on the Cl atom. The van der Waals parameters for Cl were fitted to the experimental density and heat of vaporization. The calculated hydration free energy, solvent reaction fields, and interaction energies of several homo- and heterodimer of chloromethanes are in good agreement with experimental and ab initio data. This study suggests that sophisticated electrostatic models, such as polarizable atomic multipoles, are needed for accurate description of electrostatics in organochlorine compounds and halogen bonds, although further improvement is necessary for better transferability. |
format | Online Article Text |
id | pubmed-4065202 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2014 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-40652022015-02-03 Modeling Organochlorine Compounds and the σ-Hole Effect Using a Polarizable Multipole Force Field Mu, Xiaojiao Wang, Qiantao Wang, Lee-Ping Fried, Stephen D. Piquemal, Jean-Philip Dalby, Kevin N. Ren, Pengyu J Phys Chem B [Image: see text] The charge distribution of halogen atoms on organochlorine compounds can be highly anisotropic and even display a so-called σ-hole, which leads to strong halogen bonds with electron donors. In this paper, we have systematically investigated a series of chloromethanes with one to four chloro substituents using a polarizable multipole-based molecular mechanics model. The atomic multipoles accurately reproduced the ab initio electrostatic potential around chloromethanes, including CCl(4), which has a prominent σ-hole on the Cl atom. The van der Waals parameters for Cl were fitted to the experimental density and heat of vaporization. The calculated hydration free energy, solvent reaction fields, and interaction energies of several homo- and heterodimer of chloromethanes are in good agreement with experimental and ab initio data. This study suggests that sophisticated electrostatic models, such as polarizable atomic multipoles, are needed for accurate description of electrostatics in organochlorine compounds and halogen bonds, although further improvement is necessary for better transferability. American Chemical Society 2014-02-03 2014-06-19 /pmc/articles/PMC4065202/ /pubmed/24484473 http://dx.doi.org/10.1021/jp411671a Text en Copyright © 2014 American Chemical Society Open Access on 02/03/2015 |
spellingShingle | Mu, Xiaojiao Wang, Qiantao Wang, Lee-Ping Fried, Stephen D. Piquemal, Jean-Philip Dalby, Kevin N. Ren, Pengyu Modeling Organochlorine Compounds and the σ-Hole Effect Using a Polarizable Multipole Force Field |
title | Modeling
Organochlorine Compounds and the σ-Hole
Effect Using a Polarizable Multipole Force Field |
title_full | Modeling
Organochlorine Compounds and the σ-Hole
Effect Using a Polarizable Multipole Force Field |
title_fullStr | Modeling
Organochlorine Compounds and the σ-Hole
Effect Using a Polarizable Multipole Force Field |
title_full_unstemmed | Modeling
Organochlorine Compounds and the σ-Hole
Effect Using a Polarizable Multipole Force Field |
title_short | Modeling
Organochlorine Compounds and the σ-Hole
Effect Using a Polarizable Multipole Force Field |
title_sort | modeling
organochlorine compounds and the σ-hole
effect using a polarizable multipole force field |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4065202/ https://www.ncbi.nlm.nih.gov/pubmed/24484473 http://dx.doi.org/10.1021/jp411671a |
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