Measuring Photodissociation Product Quantum Yields Using Chemical Ionization Mass Spectrometry: A Case Study with Ketones.

Measurements of photolysis quantum yields are challenging because of the difficulties in measuring the first-generation photodissociation products, interference from other products or contaminants, sufficient photon fluxes and/or low absorption cross sections of the photolyte to make detectable amounts of products, and quantification of the photon flux. In the case of acetone (and other atmospherically relevant ketones) the uncertainty in the photolysis quantum yield creates uncertainty in the calculated OH radical and acyl peroxy nitrate production in the atmosphere. We present a new method for determining photodissociation product quantum yields by measuring acyl peroxy radicals (RC(O)O2) produced in the photolysis of ketones in air using chemical ionization mass spectrometry (CIMS). We show good agreement of our CIMS method with previously published quantum yields of the acyl radical from photolysis of biacetyl and methyl ethyl ketone (MEK) at 254 nm. Additionally, we highlight the capabilities of this CIMS method through the measurement of photolysis branching ratios for MEK. We suggest future applications of CIMS (in the laboratory and field) to measure RC(O)O2 and associated photolysis processes.