Potential energy surface of the HNO + NO reaction. An ab initio molecular orbital study

Journal Article · Thu Feb 16 00:00:00 EST 1995 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100007a018· OSTI ID:6492294

Mebel, A M; Morokuma, K; Lin, M C ^[1]; Melius, C F ^[2]

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1. Emory Univ., Atlanta, GA (United States)
2. Sandia National Lab., Livermore, CA (United States)

The potential energy surface of the HNO + NO reaction has been investigated by ab initio molecular orbital calculations at the QCISD(T)/6-311G(d,p)//UMP2/6-311G(d,p) + ZPE[UMP2/6-311G(d,p)] and Gaussian-2 (G2) levels of theory. The initial reaction step is NO association with the N atom of the HNO molecule to form the HN(O)NO intermediate, 2, overcoming the barrier 1[prime] of 9.5 kcal/mol. The reaction proceeds further by 1,3-hydrogen migration in HN(O)NO from nitrogen to oxygen via the transition state 3, which is much more favorable than 1,2-shift. This step is shown to be rate-determining, having a barrier of 21.6 kcal/mol. After the H shift, trans,cis-HONNO ([sup 2]A[double prime]) intermediate, 5a, is formed, which rearranges to trans,trans-HONNO ([sup 2]A[prime]), 7b. Finally, the latter dissociates to give the reaction products H[sub 2]O + OH. The energies of the transition states for internal rearrangements of HONNO as well as the transition state for HONNO ([sup 2]A[prime]) dissociation are calculated to be significantly lower than the rate-determining barrier for 1,3-hydrogen migration in HN(O)NO. 23 refs., 2 figs., 3 tabs.

• OSTI ID: 6492294
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 99:7; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE
NITRIC OXIDE
CHEMICAL REACTIONS
NITROGEN COMPOUNDS
ISOMERIZATION
CALCULATION METHODS
CHEMICAL REACTION KINETICS
MOLECULAR ORBITAL METHOD
NITROUS OXIDE
NUMERICAL DATA
POTENTIAL ENERGY
CHALCOGENIDES
DATA
ENERGY
INFORMATION
KINETICS
NITROGEN OXIDES
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
400201* - Chemical & Physicochemical Properties
990200 - Mathematics & Computers