Acidity constants from DFT-based molecular dynamics simulations

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Marialore Sulpizi
  • Michiel Sprik
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000279257300019&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1088/0953-8984/22/28/284116
eISSN
1361-648X
Externe Identifier
  • Clarivate Analytics Document Solution ID: 617CB
  • PubMed Identifier: 21399288
ISSN
0953-8984
Ausgabe der Veröffentlichung
28
Zeitschrift
JOURNAL OF PHYSICS-CONDENSED MATTER
Artikelnummer
ARTN 284116
Datum der Veröffentlichung
2010
Status
Published
Titel
Acidity constants from DFT-based molecular dynamics simulations
Sub types
  • Article
  • Proceedings Paper
Ausgabe der Zeitschrift
22

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Autoren
  • Marialore Sulpizi
  • Michiel Sprik
DOI
10.1088/0953-8984/22/28/284116
eISSN
1361-648X
ISSN
0953-8984
Ausgabe der Veröffentlichung
28
Zeitschrift
Journal of Physics: Condensed Matter
Online publication date
2010
Paginierung
284116 - 284116
Datum der Veröffentlichung
2010
Status
Published
Herausgeber
IOP Publishing
Herausgeber URL
http://dx.doi.org/10.1088/0953-8984/22/28/284116
Datum der Datenerfassung
2020
Titel
Acidity constants from DFT-based molecular dynamics simulations
Ausgabe der Zeitschrift
22

Datenquelle: Crossref

Abstract
In this contribution we review our recently developed method for the calculation of acidity constants from density functional theory based molecular dynamics simulations. The method is based on a half reaction scheme in which protons are formally transferred from solution to the gas phase. The corresponding deprotonation free energies are computed from the vertical energy gaps for insertion or removal of protons. Combined to full proton transfer reactions, the deprotonation energies can be used to estimate relative acidity constants and also the Brønsted pK(a) when the deprotonation free energy of a hydronium ion is used as a reference. We verified the method by investigating a series of organic and inorganic acids and bases spanning a wide range of pK(a) values (20 units). The thermochemical corrections for the biasing potentials assisting and directing the insertion are discussed in some detail.
Addresses
  • Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, UK. ms647@cam.ac.uk
Autoren
  • Marialore Sulpizi
  • Michiel Sprik
DOI
10.1088/0953-8984/22/28/284116
eISSN
1361-648X
Externe Identifier
  • PubMed Identifier: 21399288
Funding acknowledgements
  • Engineering and Physical Sciences Research Council: EP/F005636/1
Open access
false
ISSN
0953-8984
Ausgabe der Veröffentlichung
28
Zeitschrift
Journal of physics. Condensed matter : an Institute of Physics journal
Schlüsselwörter
  • Acids
  • Protons
  • Gases
  • Hydrogen-Ion Concentration
  • Algorithms
  • Models, Chemical
  • Computer Simulation
Sprache
eng
Medium
Print-Electronic
Online publication date
2010
Paginierung
284116
Datum der Veröffentlichung
2010
Status
Published
Datum der Datenerfassung
2011
Titel
Acidity constants from DFT-based molecular dynamics simulations.
Sub types
  • Review
  • Journal Article
Ausgabe der Zeitschrift
22

Datenquelle: Europe PubMed Central

Abstract
In this contribution we review our recently developed method for the calculation of acidity constants from density functional theory based molecular dynamics simulations. The method is based on a half reaction scheme in which protons are formally transferred from solution to the gas phase. The corresponding deprotonation free energies are computed from the vertical energy gaps for insertion or removal of protons. Combined to full proton transfer reactions, the deprotonation energies can be used to estimate relative acidity constants and also the Brønsted pK(a) when the deprotonation free energy of a hydronium ion is used as a reference. We verified the method by investigating a series of organic and inorganic acids and bases spanning a wide range of pK(a) values (20 units). The thermochemical corrections for the biasing potentials assisting and directing the insertion are discussed in some detail.
Autoren
  • Marialore Sulpizi
  • Michiel Sprik
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/21399288
DOI
10.1088/0953-8984/22/28/284116
eISSN
1361-648X
Ausgabe der Veröffentlichung
28
Zeitschrift
J Phys Condens Matter
Schlüsselwörter
  • Acids
  • Algorithms
  • Computer Simulation
  • Gases
  • Hydrogen-Ion Concentration
  • Models, Chemical
  • Protons
Sprache
eng
Country
England
Paginierung
284116
PII
S0953-8984(10)39538-5
Datum der Veröffentlichung
2010
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2011
Titel
Acidity constants from DFT-based molecular dynamics simulations.
Sub types
  • Journal Article
  • Review
Ausgabe der Zeitschrift
22

Datenquelle: PubMed

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