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Mechanism for the gas‐phase hydrogen fluoride‐mediated decomposition of peroxyacetyl nitrate (PAN) studied by DFT method
Author(s) -
Zhao XiaoXia,
Liu FengLing
Publication year - 2010
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22224
Subject(s) - chemistry , hydrogen fluoride , fluoride , peroxyacetyl nitrate , hydrogen , decomposition , molecule , inorganic chemistry , density functional theory , proton affinity , electrophile , hydrogen atom , reaction mechanism , computational chemistry , photochemistry , catalysis , ion , organic chemistry , nox , alkyl , protonation , combustion
Abstract Density functional theory has been used to study the mechanism of the decomposition of peroxyacetyl nitrate (CH 3 C(O)OONO 2 ) 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 ON 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