Photodissociation dynamics of benzaldehyde (C6H5CHO) at 266, 248, and 193 nm

Arnab Bagchi, Yu Hsuan Huang, Z. F. Xu, P. Raghunath, Yuan T. Lee, Chi Kung Ni*, Ming-Chang Lin, Yuan-Pern Lee

*Corresponding author for this work

Research output: Contribution to journalArticle

15 Scopus citations

Abstract

The photodissociation of gaseous benzaldehyde (C6H 5CHO) at 193, 248, and 266 nm using multimass ion imaging and step-scan time-resolved Fourier-transform infrared emission techniques is investigated. We also characterize the potential energies with the CCSD(T)/6-311+G(3df,2p) method and predict the branching ratios for various channels of dissociation. Upon photolysis at 248 and 266 nm, two major channels for formation of HCO and CO, with relative branching of 0.37:0.63 and 0.20:0.80, respectively, are observed. The C6H5+HCO channel has two components with large and small recoil velocities; the rapid component with average translational energy of approximately 25 kJ mol-1 dominates. The C6H6+CO channel has a similar distribution of translational energy for these two components. IR emission from internally excited C6H5CHO, ν3 (v=1) of HCO, and levels v≤2, J≤43 of CO are observed; the latter has an average rotational energy of approximately 13 kJ mol-1 and vibrational energy of approximately 6 kJ mol-1. Upon photolysis at 193 nm, similar distributions of energy are observed, except that the C6H5+HCO channel becomes the only major channel with a branching ratio of 0.82±0.10 and an increased proportion of the slow component; IR emission from levels ν1 (v=1) and ν3 (v=1 and 2) of HCO and v≤2, J≤43 of CO are observed; the latter has an average energy similar to that observed in photolysis at 248 nm. The observed product yields at different dissociation energies are compared to statistical-theory predicted results based on the computed singlet and triplet potential-energy surfaces.

Original languageEnglish
Pages (from-to)2961-2976
Number of pages16
JournalChemistry - An Asian Journal
Volume6
Issue number11
DOIs
StatePublished - 4 Nov 2011

Keywords

  • benzaldehyde
  • computational chemistry
  • photochemistry
  • photolysis
  • time-resolved spectroscopy

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