| Molecular dynamics calculation of molecular volumes and volumes of activation. | |
| | |
MedLine Citation:
|
PMID: 22237671 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
|
Experimentally, the effects of pressure on reaction rates are described by their pressure derivatives, known as volumes of activation. Transition state theory directly links activation volumes to partial molar volumes of reactants and transition states. We discuss a molecular dynamics method for the accurate calculation of molecular volumes, within which the volumes of molecular species are obtained as a difference between the volumes of pure solvent and solvent with a single molecule inserted. The volumes thus obtained depend on the molecular geometry, the strength and type of the solute-solvent interactions, as well as temperature and pressure. The partial molar volumes calculated using this approach agree well with experimental data. Since this method can also be applied to transition state species, it allows for quantitative analysis of experimental volumes of activation in terms of structural parameters of the corresponding transition states. The efficiency of the approach is illustrated by calculation of volumes of activation for three nonpolar reactions in nonpolar solvents. The results agree well with the experimental data. |
| | |
Authors:
|
J Spooner; H Wiebe; N Boon; E Deglint; E Edwards; B Yanciw; B Patton; L Thiele; P Dance; N Weinberg |
Publication Detail:
|
Type: JOURNAL ARTICLE Date: 2012-1-12 |
Journal Detail:
|
Title: Physical chemistry chemical physics : PCCP Volume: - ISSN: 1463-9084 ISO Abbreviation: - Publication Date: 2012 Jan |
Date Detail:
|
Created Date: 2012-1-12 Completed Date: - Revised Date: - |
Medline Journal Info:
|
Nlm Unique ID: 100888160 Medline TA: Phys Chem Chem Phys Country: - |
Other Details:
|
Languages: ENG Pagination: - Citation Subset: - |
Affiliation:
|
Department of Chemistry, Simon Fraser University, Burnaby, BC V5S 1A6, Canada. |
Export Citation:
|
APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
|
|
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
Previous Document: Accuracy of referrals from an orthoptic vision screening program for 3- to 4-year-old preschool chil...
Next Document: Preparation and characterization of a thermostable enzyme (Mn-SOD) immobilized on supermagnetic nano...