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

Patricia Pérez; Renato Contreras; Arie Aizman

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

Patricia Pérez, Renato Contreras, Arie Aizman

Exact Sciences School

Research output: Contribution to journal › Article › peer-review

3 Citations (Scopus)

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 (pK_a < 0) and the weak dissociation of HF (pK_a > 0) in water.

Original language	English
Pages (from-to)	19326-19332
Number of pages	7
Journal	Journal of Physical Chemistry
Volume	100
Issue number	50
Publication status	Published - 12 Dec 1996

ASJC Scopus subject areas

Engineering(all)
Physical and Theoretical Chemistry

Cite this

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title = "Electrostatic and non-electrostatic contributions to hydrogen bonding and proton transfer in solution phase",

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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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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M3 - Article

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SN - 0022-3654

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JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 50

ER -

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

Abstract

ASJC Scopus subject areas

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