Electrostatic and non-electrostatic contributions to hydrogen bonding and proton transfer in solution phase

Patricia Pérez, Renato Contreras, Arie Aizman

Resultado de la investigación: Article

3 Citas (Scopus)

Resumen

A combined methodology of semiempirical density functional (DFT) and Hartree-Fock (HF) theories is used to analyze the solution-phase proton-transfer (PT) process in the H2O⋯HX (X = F, Cl, and OH) model systems. Gas-phase PT, hydrogen bonding, ion-pairing, dissociation, and solvent effect are considered as the contributing factors to the solution PT reaction. The H-bonded and ion-pair structures are determined from the proton-transfer potential (PTP) profiles and full geometry optimization, using the Amsterdam density functional (ADF) code. These structures are then used as input to the semiempirical SCRF/CNDO method that incorporates solvent effects. The semiempirical SCRF gas-phase results qualitatively reproduce the experimental trend for the gas-phase proton affinities (PA) (OH- > F- > Cl-). The solution-phase results correctly explain the strong acid character of HCl (pKa < 0) and the weak dissociation of HF (pKa > 0) in water.

Idioma originalEnglish
Páginas (desde-hasta)19326-19332
Número de páginas7
PublicaciónJournal of Physical Chemistry
Volumen100
N.º50
EstadoPublished - 12 dic 1996

Huella dactilar

Proton transfer
Electrostatics
Hydrogen bonds
electrostatics
protons
Gases
hydrogen
vapor phases
Ions
Protons
affinity
ions
Hydrogen
Acids
Geometry
Water
dissociation
methodology
trends
acids

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

Citar esto

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abstract = "A combined methodology of semiempirical density functional (DFT) and Hartree-Fock (HF) theories is used to analyze the solution-phase proton-transfer (PT) process in the H2O⋯HX (X = F, Cl, and OH) model systems. Gas-phase PT, hydrogen bonding, ion-pairing, dissociation, and solvent effect are considered as the contributing factors to the solution PT reaction. The H-bonded and ion-pair structures are determined from the proton-transfer potential (PTP) profiles and full geometry optimization, using the Amsterdam density functional (ADF) code. These structures are then used as input to the semiempirical SCRF/CNDO method that incorporates solvent effects. The semiempirical SCRF gas-phase results qualitatively reproduce the experimental trend for the gas-phase proton affinities (PA) (OH- > F- > Cl-). The solution-phase results correctly explain the strong acid character of HCl (pKa < 0) and the weak dissociation of HF (pKa > 0) in water.",
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Electrostatic and non-electrostatic contributions to hydrogen bonding and proton transfer in solution phase. / Pérez, Patricia; Contreras, Renato; Aizman, Arie.

En: Journal of Physical Chemistry, Vol. 100, N.º 50, 12.12.1996, p. 19326-19332.

Resultado de la investigación: Article

TY - JOUR

T1 - Electrostatic and non-electrostatic contributions to hydrogen bonding and proton transfer in solution phase

AU - Pérez, Patricia

AU - Contreras, Renato

AU - Aizman, Arie

PY - 1996/12/12

Y1 - 1996/12/12

N2 - A combined methodology of semiempirical density functional (DFT) and Hartree-Fock (HF) theories is used to analyze the solution-phase proton-transfer (PT) process in the H2O⋯HX (X = F, Cl, and OH) model systems. Gas-phase PT, hydrogen bonding, ion-pairing, dissociation, and solvent effect are considered as the contributing factors to the solution PT reaction. The H-bonded and ion-pair structures are determined from the proton-transfer potential (PTP) profiles and full geometry optimization, using the Amsterdam density functional (ADF) code. These structures are then used as input to the semiempirical SCRF/CNDO method that incorporates solvent effects. The semiempirical SCRF gas-phase results qualitatively reproduce the experimental trend for the gas-phase proton affinities (PA) (OH- > F- > Cl-). The solution-phase results correctly explain the strong acid character of HCl (pKa < 0) and the weak dissociation of HF (pKa > 0) in water.

AB - A combined methodology of semiempirical density functional (DFT) and Hartree-Fock (HF) theories is used to analyze the solution-phase proton-transfer (PT) process in the H2O⋯HX (X = F, Cl, and OH) model systems. Gas-phase PT, hydrogen bonding, ion-pairing, dissociation, and solvent effect are considered as the contributing factors to the solution PT reaction. The H-bonded and ion-pair structures are determined from the proton-transfer potential (PTP) profiles and full geometry optimization, using the Amsterdam density functional (ADF) code. These structures are then used as input to the semiempirical SCRF/CNDO method that incorporates solvent effects. The semiempirical SCRF gas-phase results qualitatively reproduce the experimental trend for the gas-phase proton affinities (PA) (OH- > F- > Cl-). The solution-phase results correctly explain the strong acid character of HCl (pKa < 0) and the weak dissociation of HF (pKa > 0) in water.

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JO - Journal of Physical Chemistry

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