THEORETICAL INVESTIGATION OF A NONADIABATIC MECHANISM FOR ALKYLPERNITRITE DECOMPOSITION
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Date
2004
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Publisher
Ohio State University
Abstract
We investigate a nonadiabatic two-state mechanism for reaction of alkylperoxyl radicals (ROO) with nitric oxide, an important step in the tropospheric ozone cycle. In our proposal, which is supported by high-level ab initio electronic structure calculations for $R = CH_{3}$, the pernitrite adduct ROONO propagates initially on a diabatic potential surface that correlates asymptotically with the $\tilde{A} ^{2}B_{2}$ state of $NO_{2}$. This potential intersects a second diabatic potential corresponding to the stable nitrate species $RNO_{2}$, which correlates with ground-state $(\tilde{X}^{2}A_{1}) NO_{2}$. Near the intersection of these two surfaces, ROONO exhibits substantial diradical character. Diabatic potentials for the model system FONO have been developed based on CCSD(T)/cc-pVTZ electronic structure calculations. Here we report the results of classical and quantum dynamics simulations for $FO + NO \rightarrow FONO \rightarrow FNO_{2}$.
Description
Author Institution: Department of Chemistry, University of California; Department of Chemistry, The Ohio State University; Department of Chemistry and Biochemistry, University of Texas