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When volatile alkenes are emitted into the atmosphere, they are rapidly removed by oxidizing agents such as hydroxyl radicals and ozone. The latter reaction is termed ozonolysis and is an important source of Criegee intermediates (CIs), i.e., carbonyl oxides, that are implicated in enhancing the oxidizing capacity of the troposphere. These CIs aid in the formation of lower volatility compounds that typically condense to form secondary organic aerosols. CIs have attracted vast attention over the past two decades. Despite this, the effect of their substitution on the ground and excited state chemistries of CIs is not well studied. Here, we extend our knowledge obtained from prior studies on CIs by CF3 substitution. The resulting CF3CHOO molecule is a CI that can be formed from the ozonolysis of hydrofluoroolefins (HFOs). Our results show that the ground state unimolecular decay should be less reactive and thus more persistent in the atmosphere than the non-fluorinated analog. The excited state dynamics, however, are predicted to occur on an ultrafast timescale. The results are discussed in the context of the ways in which our study could advance synthetic chemistry, as well as processes relevant to the atmosphere. 

Molecular spectroscopy and photochemistry constitute an integral field in modern chemistry. However, undergraduate level classes provide limited opportunities for hands-on experimentation of photochemistry and photophysics. For this reason, a simple laboratory experiment was designed that may be easily implemented into undergraduate teaching laboratories with the aim of introducing undergraduate students to UV/visible spectroscopy and photochemistry/photophysics and its possible applications. Samples of three unknown sunscreen formulations are given to students and they are asked to use a set of techniques to identify their molecular composition and to test their efficacy using basic laboratory equipment available to them. In particular, the students are asked to complete the following tasks: (i) sample preparation using solvent extraction to extract active ingredients from the sunscreen lotion, (ii) identify the extracted molecular sunscreen constituents by Thin Layer Chromatography (TLC) and UV/visible spectroscopy, and finally (iii) study their photostability by means of steady state irradiation coupled with UV/visible spectroscopy. The students were provided with the following tools for data collection: silica-backed TLC plates, a short-wave lamp (254 nm, for TLC analysis), a UV-Vis spectrophotometer with an associated computer and software, and an LED lamp (315 nm) to irradiate the samples. Combined TLC and UV-Vis spectroscopy allowed the students to identify the extracted ingredients. UV irradiation confirmed the photostability of sunscreens. 

Molecular spectroscopy and photochemistry constitute an integral field in modern chemistry. However, undergraduate level classes provide limited opportunities for hands-on experimentation of photochemistry and photophysics. For this reason, a simple laboratory experiment was designed that may be easily implemented into undergraduate teaching laboratories with the aim of introducing undergraduate students to UV/visible spectroscopy and photochemistry/photophysics and its possible applications. Samples of three unknown sunscreen formulations are given to students and they are asked to use a set of techniques to identify their molecular composition and to test their efficacy using basic laboratory equipment available to them. In particular, the students are asked to complete the following tasks: (i) sample preparation using solvent extraction to extract active ingredients from the sunscreen lotion, (ii) identify the extracted molecular sunscreen constituents by Thin Layer Chromatography (TLC) and UV/visible spectroscopy, and finally (iii) study their photostability by means of steady state irradiation coupled with UV/visible spectroscopy. The students were provided with the following tools for data collection: silica-backed TLC plates, a short-wave lamp (254 nm, for TLC analysis), a UV-Vis spectrophotometer with an associated computer and software, and an LED lamp (315 nm) to irradiate the samples. Combined TLC and UV-Vis spectroscopy allowed the students to identify the extracted ingredients. UV irradiation confirmed the photostability of sunscreens.