Photodissociation of tert-Butyl Nitrite : Investigation of Steric Influences on Vector Correlations
Birndorf, Mara D.
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Vector correlations in the photodissociation of alkyl nitrites are useful for determining reaction mechanisms. The photodissociation of tert-butyl nitrite, the topic of study in this experiment, has not been highly studied, especially through excitation to the S2 state. Due to the bulky t-butyl group, the parent molecule is constrained to the trans conformation. To show how the constraint affects the departing fragments we measured their vector correlations using polarized lasers and velocity-mapped ion imaging. We fit the ion images to a semi-classical model that quantifies the μ-v, μ-J, and v-J correlation and the (v x μ) ・ J orientation. In the experiment, tert-butyl nitrite was dissociated at 230 nm, the NO fragments probed with a 1+1′ REMPI scheme, and the fragments were subsequently velocity mapped to create ion images. Our analysis of the ion images reveal that the vector correlations in the photodissociation of tert-butyl nitrite are μ||v, μ_J, v_J. Further, the angular momentum, j, is oriented parallel to v x μ.