Role of the triplet state in gas-phase photolysis of aliphatic ketones and aldehydes

1966 ◽  
Vol 62 ◽  
pp. 2444 ◽  
Author(s):  
R. B. Cundall ◽  
A. S. Davies

The cis-trans isomerization of butene-2 has been used to measure the triplet state yields in the photolysis of acetaldehyde at various wavelengths between 313 and 254 nm over the temperature range 35 to 140 °C. The results, together with those derived from chemical product formation, are consistent with data from luminescence studies. Dissociation into molecular products occurs rapidly, probably by predissociation, from a non-quenchable excited state formed by absorption. The main free radical decomposition occurs from the triplet state and this, in the absence of additives, such as butene-2, is responsible for the chain decomposition. The intersystem crossing and non-quenchable processes are independent of temperature. Isopentyl radicals formed from methyl addition to butene-2 can also propagate a chain reaction for acetaldehyde decomposition. At high temperatures and low pressures, dissociation of vibrationally excited isopentyl radicals can contribute to the measured isomerization yield. This is shown by the effect of addition of inert gas. Evidence is put forward that geometrical isomerization of the olefin involves a triplet aldehyde-olefin complex that can be decomposed by collision with ground state aldehyde molecules without cis-trans rearrangement of the olefin. This conclusion is consistent with other work in the gas and liquid phases.


2020 ◽  
Vol 500 (3) ◽  
pp. 3414-3424
Author(s):  
Alec Paulive ◽  
Christopher N Shingledecker ◽  
Eric Herbst

ABSTRACT Complex organic molecules (COMs) have been detected in a variety of interstellar sources. The abundances of these COMs in warming sources can be explained by syntheses linked to increasing temperatures and densities, allowing quasi-thermal chemical reactions to occur rapidly enough to produce observable amounts of COMs, both in the gas phase, and upon dust grain ice mantles. The COMs produced on grains then become gaseous as the temperature increases sufficiently to allow their thermal desorption. The recent observation of gaseous COMs in cold sources has not been fully explained by these gas-phase and dust grain production routes. Radiolysis chemistry is a possible non-thermal method of producing COMs in cold dark clouds. This new method greatly increases the modelled abundance of selected COMs upon the ice surface and within the ice mantle due to excitation and ionization events from cosmic ray bombardment. We examine the effect of radiolysis on three C2H4O2 isomers – methyl formate (HCOOCH3), glycolaldehyde (HCOCH2OH), and acetic acid (CH3COOH) – and a chemically similar molecule, dimethyl ether (CH3OCH3), in cold dark clouds. We then compare our modelled gaseous abundances with observed abundances in TMC-1, L1689B, and B1-b.


2007 ◽  
Vol 52 (10) ◽  
pp. 1498-1502 ◽  
Author(s):  
V. F. Kostryukov ◽  
V. R. Pshestanchik ◽  
I. A. Donkareva ◽  
B. L. Agapov ◽  
S. I. Lopatin ◽  
...  
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