On the Theoretical Determination of Photolysis Properties for Atmospheric Volatile Organic Compounds.

Volatile organic compounds (VOCs) are ubiquitous atmospheric molecules that generate a complex network of chemical reactions in the troposphere, often triggered by the absorption of sunlight. Understanding the VOC composition of the atmosphere relies on our ability to characterize all of their possible reaction pathways. When considering reactions of (transient) VOCs with sunlight, the availability of photolysis rate constants, utilized in general atmospheric models, is often out of experimental reach due to the unstable nature of these molecules. Here, we show how recent advances in computational photochemistry allow us to calculate in silico the different ingredients of a photolysis rate constant, namely, the photoabsorption cross-section and wavelength-dependent quantum yields. The rich photochemistry of tert-butyl hydroperoxide, for which experimental data are available, is employed to test our protocol and highlight the strengths and weaknesses of different levels of electronic structure and nonadiabatic molecular dynamics to study the photochemistry of (transient) VOCs.