Acidity constants from vertical energy gaps: density functional theory based molecular dynamics implementation

Publication type:
Journal article
Metadata:
Autoren
  • Marialore Sulpizi
  • Michiel Sprik
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000258738200011&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1039/b802376j
eISSN
1463-9084
Externe Identifier
  • Clarivate Analytics Document Solution ID: 341TO
  • PubMed Identifier: 18728866
ISSN
1463-9076
Ausgabe der Veröffentlichung
34
Zeitschrift
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Paginierung
5238 - 5249
Datum der Veröffentlichung
2008
Status
Published
Titel
Acidity constants from vertical energy gaps: density functional theory based molecular dynamics implementation
Sub types
  • Article
Ausgabe der Zeitschrift
10

Data source: Web of Science (Lite)

Other metadata sources:
Autoren
  • Marialore Sulpizi
  • Michiel Sprik
DOI
10.1039/b802376j
eISSN
1463-9084
ISSN
1463-9076
Ausgabe der Veröffentlichung
34
Zeitschrift
Physical Chemistry Chemical Physics
Sprache
en
Paginierung
5238 - 5238
Datum der Veröffentlichung
2008
Status
Published
Herausgeber
Royal Society of Chemistry (RSC)
Herausgeber URL
http://dx.doi.org/10.1039/b802376j
Datum der Datenerfassung
2024
Titel
Acidity constants from vertical energy gaps: density functional theory based molecular dynamics implementation
Ausgabe der Zeitschrift
10

Data source: Crossref

Abstract
The question of how to compute acidity constants (pKa) treating solvent and solute at the same level of theory remains of some interest, for example in the case of high or low pH conditions. We have developed a density functional theory based molecular dynamics implementation of such a method. The method is based on a half reaction scheme computing free energies of dissociation from the vertical energy gaps for insertion or removal of protons. Finite system size effects are important, but largely cancel when half reactions are combined to full reactions. We verified the method by investigating a series of organic and inorganic acids and bases spanning a wide range of pKa values (20 units). We find that the response of the aqueous solvent to vertical protonation/deprotonation is almost always asymmetric and correlated with the strength of the hydrogen bonding of the deprotonated base. We interpret these observations in analogy with the picture of solvent response to electronic ionization.
Addresses
  • Department of Chemistry, University of Cambridge, Cambridge, United Kingdom. ms647@cam.ac.uk
Autoren
  • Marialore Sulpizi
  • Michiel Sprik
DOI
10.1039/b802376j
eISSN
1463-9084
Externe Identifier
  • PubMed Identifier: 18728866
Open access
false
ISSN
1463-9076
Ausgabe der Veröffentlichung
34
Zeitschrift
Physical chemistry chemical physics : PCCP
Sprache
eng
Medium
Print-Electronic
Online publication date
2008
Paginierung
5238 - 5249
Datum der Veröffentlichung
2008
Status
Published
Datum der Datenerfassung
2008
Titel
Acidity constants from vertical energy gaps: density functional theory based molecular dynamics implementation.
Sub types
  • Research Support, Non-U.S. Gov't
  • Journal Article
Ausgabe der Zeitschrift
10

Data source: Europe PubMed Central

Abstract
The question of how to compute acidity constants (pKa) treating solvent and solute at the same level of theory remains of some interest, for example in the case of high or low pH conditions. We have developed a density functional theory based molecular dynamics implementation of such a method. The method is based on a half reaction scheme computing free energies of dissociation from the vertical energy gaps for insertion or removal of protons. Finite system size effects are important, but largely cancel when half reactions are combined to full reactions. We verified the method by investigating a series of organic and inorganic acids and bases spanning a wide range of pKa values (20 units). We find that the response of the aqueous solvent to vertical protonation/deprotonation is almost always asymmetric and correlated with the strength of the hydrogen bonding of the deprotonated base. We interpret these observations in analogy with the picture of solvent response to electronic ionization.
Autoren
  • Marialore Sulpizi
  • Michiel Sprik
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/18728866
DOI
10.1039/b802376j
ISSN
1463-9076
Ausgabe der Veröffentlichung
34
Zeitschrift
Phys Chem Chem Phys
Sprache
eng
Country
England
Paginierung
5238 - 5249
Datum der Veröffentlichung
2008
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2008
Titel
Acidity constants from vertical energy gaps: density functional theory based molecular dynamics implementation.
Sub types
  • Journal Article
  • Research Support, Non-U.S. Gov't
Ausgabe der Zeitschrift
10

Data source: PubMed

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