DYNAMICS OF EXCITED STATES OF CH2OO, CH3CHOO AND (CH3)2COO KRIEGE INTERMEDIATES

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Abstract

Carbonyl oxides, or Criegee intermediates, are chemically active compounds that readily react with other atmospheric components, promoting the formation of OH and CH3 radicals, nitrogen oxides, aldehydes, hydrogen peroxide, and various acids. In this work, we consider the physicochemical processes involving electronically excited states of three simple Criegee intermediates: CH2OO, CH3CHOO and (CH3)2COO. In addition to the ground state S0, the calculation scheme included four low-lying excited electronic states: S1 (nπ*), S2 (ππ*), S3 (nπ*), and S4 (ππ*). It was found that the optical transitions S0→S2 and S0→S4 have comparatively large dipole moments; therefore, they are observed in the absorption spectra of these compounds and play a key role in atmospheric processes. Analysis of the PES structures corresponding to these excited states, their relative arrangement, local minima and maxima, as well as intersection points, showed that under photoexcitation in typical atmospheric conditions the most probable chemical reaction is direct O—O bond cleavage in the S2 (ππ*) or S4 (ππ*) states, leading to oxygen atom detachment O(1D). Under more complex conditions, when the molecule possesses a sufficient amount of internal energy, transitions to lower-lying electronic states are possible, whose equilibrium geometries strongly differ from the initial ones. This results in the release of a large amount of energy and subsequent relaxation of the molecule into the ground electronic state S0.

About the authors

Y. A. Dyakov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: yuri_dyakov@mail.ru
Moscow, Russia

N. I. Butkovskaya

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: email@example.com
Moscow, Russia

E. S. Vasiliev

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: email@example.com
Moscow, Russia

I. D. Rodionov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: email@example.com
Moscow, Russia

P. S. Khomyakova

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: email@example.com
Moscow, Russia

M. G. Golubkov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: email@example.com
Moscow, Russia

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