Employment of quantum chemical descriptors for hammett constants: Revision Suggested for the acetoxy substituent

Tamara Papp, L. Kollár, T. Kégl

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The Hammett para constant (σ of the acetoxy group has been estimated by applying widely available quantum chemical descriptors, such as NPA charges, Wiberg bond indices, electron densities at bond critical points, as well as electrostatic potential at nuclei. The revised σvalue is predicted to be in the range of [-0.08,-0.02]. Direct evaluation of proton transfer free energies between the substituted benzoic acids and the benzoate anion by employing the SMD solvation model resulted in a reasonable linear correlation with the Hammett constants with a prediction of σ= -0.02 for the OAc group.

Original languageEnglish
Pages (from-to)51-56
Number of pages6
JournalChemical Physics Letters
Volume588
DOIs
Publication statusPublished - Nov 19 2013

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Benzoates
Proton transfer
Surface mount technology
Solvation
benzoic acid
Free energy
Anions
Carrier concentration
solvation
Electrostatics
critical point
free energy
electrostatics
anions
nuclei
protons
evaluation
predictions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

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abstract = "The Hammett para constant (σ of the acetoxy group has been estimated by applying widely available quantum chemical descriptors, such as NPA charges, Wiberg bond indices, electron densities at bond critical points, as well as electrostatic potential at nuclei. The revised σvalue is predicted to be in the range of [-0.08,-0.02]. Direct evaluation of proton transfer free energies between the substituted benzoic acids and the benzoate anion by employing the SMD solvation model resulted in a reasonable linear correlation with the Hammett constants with a prediction of σ= -0.02 for the OAc group.",
author = "Tamara Papp and L. Koll{\'a}r and T. K{\'e}gl",
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AU - Papp, Tamara

AU - Kollár, L.

AU - Kégl, T.

PY - 2013/11/19

Y1 - 2013/11/19

N2 - The Hammett para constant (σ of the acetoxy group has been estimated by applying widely available quantum chemical descriptors, such as NPA charges, Wiberg bond indices, electron densities at bond critical points, as well as electrostatic potential at nuclei. The revised σvalue is predicted to be in the range of [-0.08,-0.02]. Direct evaluation of proton transfer free energies between the substituted benzoic acids and the benzoate anion by employing the SMD solvation model resulted in a reasonable linear correlation with the Hammett constants with a prediction of σ= -0.02 for the OAc group.

AB - The Hammett para constant (σ of the acetoxy group has been estimated by applying widely available quantum chemical descriptors, such as NPA charges, Wiberg bond indices, electron densities at bond critical points, as well as electrostatic potential at nuclei. The revised σvalue is predicted to be in the range of [-0.08,-0.02]. Direct evaluation of proton transfer free energies between the substituted benzoic acids and the benzoate anion by employing the SMD solvation model resulted in a reasonable linear correlation with the Hammett constants with a prediction of σ= -0.02 for the OAc group.

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