Photodissociation Dynamics of Benzaldehyde-d5 at 205 nm:The H Atom Production Channel

초록

Photodissociation dynamics of benzaldehyde-d(5) (C6D5CHO) at 205 nm was investigated by measuring laser-induced fluorescence spectra of fragment H atoms. From the Doppler-broadened spectra, center-of-mass translational energy release into the C6D5CO + H channel was obtained as 68.8 +/- 5.8 kJ/mol with the absolute quantum yield, 0.17 +/- 0.03. The observed translational energy was successfully estimated from two-dimensional potential energy surfaces along the C-H dissociation coordinate and the CCO bent angle and the out-of-plane H angle, respectively calculated at the B3LYP/cc-pVDZ level. The dissociation of H should take place along the triplet surface via intersystem crossing from S-1 after internal conversion from the initially excited S-3 state and on the triplet surface, the dissociation proceeds along the CCO bent-linear-bent configuration with H being planar to nonplanar pathway.

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