New Mechanism of Singlet Oxygen Production in Processes with Participation of Electronically and Vibrationally Excited Ozone Moleculesстатья

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[1] New mechanism of singlet oxygen production in processes with participation of electronically and vibrationally excited ozone molecules / K. S. Klopovskii, A. S. Kovalev, D. V. Lopaev et al. // JETF. — 1995. — Vol. 80, no. 4. — P. 603–613. A theoretical model of the production of oxygen molecules in the lower singlet state alAg in excited nitrogen-oxygen gaseous media is presented. The model includes a new mechanism of ∼∼(a' A,) production by means of energy transfer accompanying the interaction of the electronically excited 13B2 state of ozone with ground-state oxygen molecules. It is shown that ozone molecules in the state are produced mainly by nonadiabatic transitions from the 'A ground state as a result of strong excitation of asymmetric vibrations of 03. It is shown that vibrationally excited nitrogen plays an important role as a reservoir for asymmetric vibrations of ozone. The observed acceleration of the quenching of oz(alAg) molecules in reactions with ozone is associated with the excitation of bending vibrations of O3 and probably proceeds via the excitation of the intermediate electronic state 03(13B2). The rate constants for previously unknown processes were determined by comparing the modeling results to experimental data. Values were obtained for the rate constants of vv' exchange between NZ(v= 1) and 03(101) and for quasiresonant transfer of electronic excitation from 03(13∼,) to O∼(U'A,): (5 +2). 10-l4 cm3/s and (1.420.5). 10-l2 cm3/s, respectively.

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