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

Journal Article · Thu Feb 16 04:00:00 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), Journal Name: Journal of Physical Chemistry; (United States) Vol. 99:7; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

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