Dynamics of multi-channel dissociation of tetrahydrofuran photoexcited at 193 nm: distributions of kinetic energy, angular anisotropies and branching ratios

Literature Information

Publication Date 2010-01-27
DOI 10.1039/B921219A
Impact Factor 3.676
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Abstract

We investigated the photodissociation dynamics of tetrahydrofuran (c-C4H8O) at 193.3 nm in a molecular-beam apparatus using photofragment-translational spectroscopy and direct vacuum-ultraviolet (VUV) photoionization. Five dissociation channels leading to products with m/z ratios appropriate for CH2CH2CH2 + H2CO, CH2CHCH2 + CH2OH, H + CH2CH2 + CH2CHO, CH2CH2 + CH3 + HCO and CH2CH2 + CH2CO + H2 were identified; their branching ratios were determined to be 0.40, 0.25, 0.04 0.29 and 0.02, respectively. Secondary dissociations from nascent products CH2CH2CH2CHO to CH2CH2 + CH2CHO and from CH2CH2O to CH3 + HCO and likely to CH2CO + H2 were observed. We measured distributions of product kinetic energy, average kinetic-energy release, and fractions in translation for each dissociation channel. The formation of CH2CHCH2 + CH2OH indicates that hydrogen migration occurs before complete fragmentation. All photofragments have nearly isotropic angular distributions, with |β| values less than 0.05. The photodissociation of tetrahydrofuran into five channels is proposed to proceed mainly on the ground state potential-energy surface following ring opening and efficient internal conversions.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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