How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents?
Autor(a) principal: | |
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Data de Publicação: | 2016 |
Outros Autores: | , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Journal of the Brazilian Chemical Society (Online) |
Texto Completo: | http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532016001102055 |
Resumo: | In the past seven years, the SMD (Solvent Model Density) method has been widely used by computational chemists. Thus, assessment on the reliability of this model for modeling chemical process in solution is worthwhile. In this report, it was investigated six anion-molecule nucleophilic substitution reactions in methanol and dipolar aprotic solvents. Geometry optimizations have been done at SMD/X3LYP level and single point energy calculations at CCSD(T)/TZVPP + diff level. Our results have indicated that the SMD model is not adequate for dipolar aprotic solvents, with a root of mean squared (RMS) error of 5.6 kcal mol-1, while the Polarizable Continuum Model (PCM) method with the Pliego and Riveros atomic cavities has led to RMS error of only 3.2 kcal mol-1. For methanol solvent, the SMD method has a RMS error of 3.0 kcal mol-1. The classical protic to dipolar aprotic solvent rate acceleration effect was not predicted by the SMD model for the tested systems. |
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How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents?continuum solvation modelion solvationsolvent effectaromatic nucleophilic substitutionM11 functionalIn the past seven years, the SMD (Solvent Model Density) method has been widely used by computational chemists. Thus, assessment on the reliability of this model for modeling chemical process in solution is worthwhile. In this report, it was investigated six anion-molecule nucleophilic substitution reactions in methanol and dipolar aprotic solvents. Geometry optimizations have been done at SMD/X3LYP level and single point energy calculations at CCSD(T)/TZVPP + diff level. Our results have indicated that the SMD model is not adequate for dipolar aprotic solvents, with a root of mean squared (RMS) error of 5.6 kcal mol-1, while the Polarizable Continuum Model (PCM) method with the Pliego and Riveros atomic cavities has led to RMS error of only 3.2 kcal mol-1. For methanol solvent, the SMD method has a RMS error of 3.0 kcal mol-1. The classical protic to dipolar aprotic solvent rate acceleration effect was not predicted by the SMD model for the tested systems.Sociedade Brasileira de Química2016-11-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532016001102055Journal of the Brazilian Chemical Society v.27 n.11 2016reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.5935/0103-5053.20160095info:eu-repo/semantics/openAccessMiguel,Elizabeth L. M.Santos,Calink I. L.Silva,Carlos M.Pliego Jr.,Josefredo R.eng2016-11-04T00:00:00Zoai:scielo:S0103-50532016001102055Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2016-11-04T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false |
dc.title.none.fl_str_mv |
How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents? |
title |
How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents? |
spellingShingle |
How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents? Miguel,Elizabeth L. M. continuum solvation model ion solvation solvent effect aromatic nucleophilic substitution M11 functional |
title_short |
How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents? |
title_full |
How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents? |
title_fullStr |
How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents? |
title_full_unstemmed |
How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents? |
title_sort |
How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents? |
author |
Miguel,Elizabeth L. M. |
author_facet |
Miguel,Elizabeth L. M. Santos,Calink I. L. Silva,Carlos M. Pliego Jr.,Josefredo R. |
author_role |
author |
author2 |
Santos,Calink I. L. Silva,Carlos M. Pliego Jr.,Josefredo R. |
author2_role |
author author author |
dc.contributor.author.fl_str_mv |
Miguel,Elizabeth L. M. Santos,Calink I. L. Silva,Carlos M. Pliego Jr.,Josefredo R. |
dc.subject.por.fl_str_mv |
continuum solvation model ion solvation solvent effect aromatic nucleophilic substitution M11 functional |
topic |
continuum solvation model ion solvation solvent effect aromatic nucleophilic substitution M11 functional |
description |
In the past seven years, the SMD (Solvent Model Density) method has been widely used by computational chemists. Thus, assessment on the reliability of this model for modeling chemical process in solution is worthwhile. In this report, it was investigated six anion-molecule nucleophilic substitution reactions in methanol and dipolar aprotic solvents. Geometry optimizations have been done at SMD/X3LYP level and single point energy calculations at CCSD(T)/TZVPP + diff level. Our results have indicated that the SMD model is not adequate for dipolar aprotic solvents, with a root of mean squared (RMS) error of 5.6 kcal mol-1, while the Polarizable Continuum Model (PCM) method with the Pliego and Riveros atomic cavities has led to RMS error of only 3.2 kcal mol-1. For methanol solvent, the SMD method has a RMS error of 3.0 kcal mol-1. The classical protic to dipolar aprotic solvent rate acceleration effect was not predicted by the SMD model for the tested systems. |
publishDate |
2016 |
dc.date.none.fl_str_mv |
2016-11-01 |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532016001102055 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532016001102055 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.5935/0103-5053.20160095 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
text/html |
dc.publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
dc.source.none.fl_str_mv |
Journal of the Brazilian Chemical Society v.27 n.11 2016 reponame:Journal of the Brazilian Chemical Society (Online) instname:Sociedade Brasileira de Química (SBQ) instacron:SBQ |
instname_str |
Sociedade Brasileira de Química (SBQ) |
instacron_str |
SBQ |
institution |
SBQ |
reponame_str |
Journal of the Brazilian Chemical Society (Online) |
collection |
Journal of the Brazilian Chemical Society (Online) |
repository.name.fl_str_mv |
Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ) |
repository.mail.fl_str_mv |
||office@jbcs.sbq.org.br |
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1750318178793160704 |