Theoretical investigation of the potential energy surface for the reactionof NO3 with H

Citation
Lc. Jitariu et Dm. Hirst, Theoretical investigation of the potential energy surface for the reactionof NO3 with H, PCCP PHYS C, 1(6), 1999, pp. 983-987
Citations number
21
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
PCCP PHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN journal
14639076 → ACNP
Volume
1
Issue
6
Year of publication
1999
Pages
983 - 987
Database
ISI
SICI code
1463-9076(19990315)1:6<983:TIOTPE>2.0.ZU;2-C
Abstract
Adducts and transition states have been located in ab initio MP2/6-311G** c alculations on both the singlet and triplet potential energy surfaces for t he reaction NO3 + H bar right arrow NO2 + OH. Reaction on the singlet surfa ce is shown to be improbable because the calculated enthalpy of activation for the initial step is about 350 kJ mol(-1). On the triplet surface an H . .. ONO2 adduct is formed exothermically without any activation barrier. In the adduct, the NO3 moiety is non-planar. Reaction on the triplet surface t o NO2 + OH can then occur via a transition state lying 16 kJ mol(-1) above the energy of the adduct.