A Theoretical Investigation of Gas Phase NO3 Initiated Nitration of p-Cresol

Carina Ebbesen Jessen; Allan Gross; Jacob Kongsted; Solvejg Jørgensen

A Theoretical Investigation of Gas Phase NO3 Initiated Nitration of p-Cresol

Carina Ebbesen Jessen, Allan Gross, Jacob Kongsted, Solvejg Jørgensen

Department of Chemistry

10 Citations (Scopus)

Abstract

The reaction mechanisms for nitration of p-cresol (4-methylphenol) initiated by the NO₃ radical are investigated theoretically. We have considered two reaction mechanisms: addition-elimination and hydrogen abstraction. Density functional theory methods employing the B3LYP and BB1K exchange-correlation functionals combined with the basis set 6-311+G(d,p) were employed for the geometry optimization of the stationary points along the reaction path. The energies have been refined using the coupled cluster singles and doubles method including a perturbative correction due to triples excitations (CCSD(T)). The barrier heights for these reaction paths are calculated in order to identify the reaction channel. The reaction path where the NO₃ radical is added to the C1 position and the NO₂ radical to the C2 position has the lowest energy barrier for the elimination of the HNO₃ and the transition state is better stabilized than any of the other transition states describing elimination.

Original language	English
Journal	Chemical Physics
Volume	389
Pages (from-to)	39-46
ISSN	0301-0104
Publication status	Published - 7 Nov 2011

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title = "A Theoretical Investigation of Gas Phase NO3 Initiated Nitration of p-Cresol",

abstract = "The reaction mechanisms for nitration of p-cresol (4-methylphenol) initiated by the NO3 radical are investigated theoretically. We have considered two reaction mechanisms: addition-elimination and hydrogen abstraction. Density functional theory methods employing the B3LYP and BB1K exchange-correlation functionals combined with the basis set 6-311+G(d,p) were employed for the geometry optimization of the stationary points along the reaction path. The energies have been refined using the coupled cluster singles and doubles method including a perturbative correction due to triples excitations (CCSD(T)). The barrier heights for these reaction paths are calculated in order to identify the reaction channel. The reaction path where the NO3 radical is added to the C1 position and the NO2 radical to the C2 position has the lowest energy barrier for the elimination of the HNO3 and the transition state is better stabilized than any of the other transition states describing elimination.",

author = "Jessen, {Carina Ebbesen} and Allan Gross and Jacob Kongsted and Solvejg J{\o}rgensen",

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T1 - A Theoretical Investigation of Gas Phase NO3 Initiated Nitration of p-Cresol

AU - Jessen, Carina Ebbesen

AU - Gross, Allan

AU - Kongsted, Jacob

AU - Jørgensen, Solvejg

PY - 2011/11/7

Y1 - 2011/11/7

N2 - The reaction mechanisms for nitration of p-cresol (4-methylphenol) initiated by the NO3 radical are investigated theoretically. We have considered two reaction mechanisms: addition-elimination and hydrogen abstraction. Density functional theory methods employing the B3LYP and BB1K exchange-correlation functionals combined with the basis set 6-311+G(d,p) were employed for the geometry optimization of the stationary points along the reaction path. The energies have been refined using the coupled cluster singles and doubles method including a perturbative correction due to triples excitations (CCSD(T)). The barrier heights for these reaction paths are calculated in order to identify the reaction channel. The reaction path where the NO3 radical is added to the C1 position and the NO2 radical to the C2 position has the lowest energy barrier for the elimination of the HNO3 and the transition state is better stabilized than any of the other transition states describing elimination.

AB - The reaction mechanisms for nitration of p-cresol (4-methylphenol) initiated by the NO3 radical are investigated theoretically. We have considered two reaction mechanisms: addition-elimination and hydrogen abstraction. Density functional theory methods employing the B3LYP and BB1K exchange-correlation functionals combined with the basis set 6-311+G(d,p) were employed for the geometry optimization of the stationary points along the reaction path. The energies have been refined using the coupled cluster singles and doubles method including a perturbative correction due to triples excitations (CCSD(T)). The barrier heights for these reaction paths are calculated in order to identify the reaction channel. The reaction path where the NO3 radical is added to the C1 position and the NO2 radical to the C2 position has the lowest energy barrier for the elimination of the HNO3 and the transition state is better stabilized than any of the other transition states describing elimination.

M3 - Journal article

SN - 0301-0104

VL - 389

SP - 39

EP - 46

JO - Chemical Physics

JF - Chemical Physics

ER -

A Theoretical Investigation of Gas Phase NO3 Initiated Nitration of p-Cresol

Abstract

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