Mechanism for the gas-phase hydrogen fluoride-mediated decomposition of peroxyacetyl nitrate (PAN) studied by DFT method

Density functional theory has been used to study the mechanism of the decomposition of peroxyacetyl nitrate (CH3C(O)OONO2) in hydrogen fluoride clusters containing one to three hydrogen fluoride molecules at the B3LYP/6‐311++G(d,p) and B3LYP/6‐311+G(3df,3pd) levels. The calculations clarify some of...

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Published in:International journal of quantum chemistry 2010-05, Vol.110 (6), p.1214-1223
Main Authors: Zhao, Xiao-Xia, Liu, Feng-Ling
Format: Article
Language:English
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decomposition
PAN
proton transfer
small hydrogen fluoride clusters
transition state
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description Density functional theory has been used to study the mechanism of the decomposition of peroxyacetyl nitrate (CH3C(O)OONO2) in hydrogen fluoride clusters containing one to three hydrogen fluoride molecules at the B3LYP/6‐311++G(d,p) and B3LYP/6‐311+G(3df,3pd) levels. The calculations clarify some of the uncertainties in the mechanism of PAN decomposition in the gas phase. The energy barrier decreases from 30.5 kcal mol−1 (single hydrogen fluoride) to essentially 18.5 kcal mol−1 when catalyzed by three hydrogen fluoride molecules. As the size of the hydrogen fluoride cluster is increased, PAN shows increasing ionization along the ON bond, consistent with the proposed predissociation in which the electrophilicity of the nitrogen atom is enhanced. This reaction is found to proceed through an attack of a fluorine to the PAN nitrogen in concert with a proton transfer to a PAN oxygen. On the basis of our calculations, an alternative reaction mechanism for the decomposition of PAN is proposed. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010
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The calculations clarify some of the uncertainties in the mechanism of PAN decomposition in the gas phase. The energy barrier decreases from 30.5 kcal mol−1 (single hydrogen fluoride) to essentially 18.5 kcal mol−1 when catalyzed by three hydrogen fluoride molecules. As the size of the hydrogen fluoride cluster is increased, PAN shows increasing ionization along the ON bond, consistent with the proposed predissociation in which the electrophilicity of the nitrogen atom is enhanced. This reaction is found to proceed through an attack of a fluorine to the PAN nitrogen in concert with a proton transfer to a PAN oxygen. On the basis of our calculations, an alternative reaction mechanism for the decomposition of PAN is proposed. © 2009 Wiley Periodicals, Inc. 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J. Quantum Chem</addtitle><description>Density functional theory has been used to study the mechanism of the decomposition of peroxyacetyl nitrate (CH3C(O)OONO2) in hydrogen fluoride clusters containing one to three hydrogen fluoride molecules at the B3LYP/6‐311++G(d,p) and B3LYP/6‐311+G(3df,3pd) levels. The calculations clarify some of the uncertainties in the mechanism of PAN decomposition in the gas phase. The energy barrier decreases from 30.5 kcal mol−1 (single hydrogen fluoride) to essentially 18.5 kcal mol−1 when catalyzed by three hydrogen fluoride molecules. As the size of the hydrogen fluoride cluster is increased, PAN shows increasing ionization along the ON bond, consistent with the proposed predissociation in which the electrophilicity of the nitrogen atom is enhanced. This reaction is found to proceed through an attack of a fluorine to the PAN nitrogen in concert with a proton transfer to a PAN oxygen. On the basis of our calculations, an alternative reaction mechanism for the decomposition of PAN is proposed. © 2009 Wiley Periodicals, Inc. 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subjects decomposition
PAN
proton transfer
small hydrogen fluoride clusters
transition state
title Mechanism for the gas-phase hydrogen fluoride-mediated decomposition of peroxyacetyl nitrate (PAN) studied by DFT method
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