Pressure and temperature dependent photolysis of glyoxal in the 355–414 nm region: evidence for dissociation from multiple states

Literature Information

Publication Date 2013-03-18
DOI 10.1039/C3CP43596B
Impact Factor 3.676
Authors

Robert J. Salter, Mark A. Blitz, Dwayne E. Heard, Michael J. Pilling, Paul W. Seakins


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Abstract

The photolysis of glyoxal has been investigated in the 355–414 nm region by dye laser photolysis coupled with cavity ring-down spectroscopy. Absolute quantum yields of HCO, ΦHCO, were determined using the reaction of chlorine atoms with formaldehyde as an actinometer. The dependence of the quantum yield on pressure was investigated in 3–400 Torr of nitrogen buffer gas and at four temperatures: 233 K, 268 K, 298 K and 323 K. For 355 nm ≤ λ < 395 nm the HCO quantum yield is pressure dependent with linear Stern–Volmer (SV) plots (1/ΦHCOvs. pressure). The zero pressure quantum yield, obtained by extrapolation of the SV plots, rises from 1.6 to 2 between 355 and 382 nm and remains at 2 up to 395 nm. For λ ≥ 395 nm ΦHCO shows a stronger pressure dependence and non-linear SV plots, compatible with formation of HCO by dissociation from two electronic states of glyoxal with significantly different lifetimes. These observations are used to develop a mechanism for the photolysis of glyoxal over the wavelength range studied.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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