Molecular electrostatics, energetics, and dynamics of the alkylation of naphthalene: Positional isomerization of monoalkylnaphthalenes at hartree-fock and correlated levels with BSSE corrections

G. Tasi, Fujio Mizukami, Makoto Toba, S. I. Niwa, I. Pálinkó

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Abstract

The energetics and dynamics of the protonation of the naphthalene molecule were investigated at the Hartree-Fock (HF) and correlated levels. Calculations at correlated levels reproduced the experimental gas-phase proton affinity and basicity of naphthalene quite well. Positional isomerizations of monoalkylnaphthalenes were studied at various theoretical levels. The calculated thermodynamic equilibrium compositions at correlated levels are in good agreement with the experimental results. According to the calculations, intramolecular shifts are possible for the methyl, ethyl, and isopropyl groups. By contrast, the bulky tert-butyl group transfers exclusively intermolecularly. In accordance with the experimental results, the activation energies of the 1,2-alkyl shifts decrease with the increase in the size of the alkyl group. This indicates that the rate-determining step of the isomerization reactions is the rearrangement of the monoalkylnaphthalenium ions via 1,2-alkyl shifts. An intermolecular methyl group transfer between two naphthalene molecules is energetically much less favored than the relevant intramolecular one. However, an appropriate basis set superposition error correction to the total energy of the three-body transition state complex is of utmost importance at second-order Møller-Plesset level.

Original languageEnglish
Pages (from-to)1337-1345
Number of pages9
JournalJournal of Physical Chemistry A
Volume104
Issue number6
Publication statusPublished - Feb 17 2000

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alkylation
Alkylation
Isomerization
naphthalene
isomerization
Electrostatics
electrostatics
Molecules
Protonation
Error correction
Alkalinity
shift
Protons
Activation energy
Gases
Thermodynamics
Ions
thermodynamic equilibrium
affinity
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Molecular electrostatics, energetics, and dynamics of the alkylation of naphthalene: Positional isomerization of monoalkylnaphthalenes at hartree-fock and correlated levels with BSSE corrections",
abstract = "The energetics and dynamics of the protonation of the naphthalene molecule were investigated at the Hartree-Fock (HF) and correlated levels. Calculations at correlated levels reproduced the experimental gas-phase proton affinity and basicity of naphthalene quite well. Positional isomerizations of monoalkylnaphthalenes were studied at various theoretical levels. The calculated thermodynamic equilibrium compositions at correlated levels are in good agreement with the experimental results. According to the calculations, intramolecular shifts are possible for the methyl, ethyl, and isopropyl groups. By contrast, the bulky tert-butyl group transfers exclusively intermolecularly. In accordance with the experimental results, the activation energies of the 1,2-alkyl shifts decrease with the increase in the size of the alkyl group. This indicates that the rate-determining step of the isomerization reactions is the rearrangement of the monoalkylnaphthalenium ions via 1,2-alkyl shifts. An intermolecular methyl group transfer between two naphthalene molecules is energetically much less favored than the relevant intramolecular one. However, an appropriate basis set superposition error correction to the total energy of the three-body transition state complex is of utmost importance at second-order M{\o}ller-Plesset level.",
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T1 - Molecular electrostatics, energetics, and dynamics of the alkylation of naphthalene

T2 - Positional isomerization of monoalkylnaphthalenes at hartree-fock and correlated levels with BSSE corrections

AU - Tasi, G.

AU - Mizukami, Fujio

AU - Toba, Makoto

AU - Niwa, S. I.

AU - Pálinkó, I.

PY - 2000/2/17

Y1 - 2000/2/17

N2 - The energetics and dynamics of the protonation of the naphthalene molecule were investigated at the Hartree-Fock (HF) and correlated levels. Calculations at correlated levels reproduced the experimental gas-phase proton affinity and basicity of naphthalene quite well. Positional isomerizations of monoalkylnaphthalenes were studied at various theoretical levels. The calculated thermodynamic equilibrium compositions at correlated levels are in good agreement with the experimental results. According to the calculations, intramolecular shifts are possible for the methyl, ethyl, and isopropyl groups. By contrast, the bulky tert-butyl group transfers exclusively intermolecularly. In accordance with the experimental results, the activation energies of the 1,2-alkyl shifts decrease with the increase in the size of the alkyl group. This indicates that the rate-determining step of the isomerization reactions is the rearrangement of the monoalkylnaphthalenium ions via 1,2-alkyl shifts. An intermolecular methyl group transfer between two naphthalene molecules is energetically much less favored than the relevant intramolecular one. However, an appropriate basis set superposition error correction to the total energy of the three-body transition state complex is of utmost importance at second-order Møller-Plesset level.

AB - The energetics and dynamics of the protonation of the naphthalene molecule were investigated at the Hartree-Fock (HF) and correlated levels. Calculations at correlated levels reproduced the experimental gas-phase proton affinity and basicity of naphthalene quite well. Positional isomerizations of monoalkylnaphthalenes were studied at various theoretical levels. The calculated thermodynamic equilibrium compositions at correlated levels are in good agreement with the experimental results. According to the calculations, intramolecular shifts are possible for the methyl, ethyl, and isopropyl groups. By contrast, the bulky tert-butyl group transfers exclusively intermolecularly. In accordance with the experimental results, the activation energies of the 1,2-alkyl shifts decrease with the increase in the size of the alkyl group. This indicates that the rate-determining step of the isomerization reactions is the rearrangement of the monoalkylnaphthalenium ions via 1,2-alkyl shifts. An intermolecular methyl group transfer between two naphthalene molecules is energetically much less favored than the relevant intramolecular one. However, an appropriate basis set superposition error correction to the total energy of the three-body transition state complex is of utmost importance at second-order Møller-Plesset level.

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