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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...

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Autores principales: Mu, Xiaojiao, Wang, Qiantao, Wang, Lee-Ping, Fried, Stephen D., Piquemal, Jean-Philip, Dalby, Kevin N., Ren, Pengyu
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
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.
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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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