Photodissociation dynamics of tert-butyl hydroperoxide at 266 nm

초록

Photodissociation dynamics of tert-butyl hydroperoxide at 266 nm was investigated by measuring laser-induced fluorescence spectra of OH fragments. The OH fragments were produced exclusively in the X2∏ states and spin-orbit ratios show approximately equal populations in the 2∏<inf>3/2</inf> and 2∏<inf>1/2</inf> states of OH. On the other hand, Λ-doublets favor the asymmetric A″ level for all measured values of N″. The distribution of total available energy among various degrees of freedom of products was found to be f<inf>rot</inf>(OH) = 0.06 ± 0.01, f<inf>trans</inf> = 0.51 ± 0.05, f<inf>int</inf> (t-BuO) = 0.43 ± 0.06, with negligible fraction of OH being produced in the vibrationally excited states. By analyzing Doppler profiles of the rotationally resolved OH spectra, vector correlations in the photodissociation of tert-butyl hydroperoxide were measured. The measured v-J correlation was positive and increased as N″ increased. From this observation and A-doublet preference, it was concluded that the parent torsional motion plays an important role in the rotational excitation of the OH fragment. © 2002 Elsevier Science B.V. All rights reserved.

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