Wiley-VCH Verlag, ChemInform, 5(40), 2009
Elsevier, Advances in Quantum Chemistry, p. 245-274
DOI: 10.1016/s0065-3276(07)00212-2
Full text: Unavailable
In the last few decades there has been an increasing concern for the environment, worldwide. The scientific community has actively contributed to the efforts to understand the chemical processes that impact our surroundings, as the vast amount of publications in this area shows. There is considerable current interest in the high levels of oxygenated compounds which are both emitted and formed in the troposphere. Their main sink involves in most cases their reactions with OH radicals, at least at daytimes. Since the OH radical has a rather large electric dipole moment it is clearly capable of forming strong hydrogen bonds. In this work, we examine the relevance of such interactions in the reactions of this radical with different oxygenated volatile organic compounds (VOCs). According to the available data, at the present time, it seems well established that these reactions take place through a complex mechanism, with a first step involving the formation of reactant complexes, caused by hydrogen bond like interactions. These interactions can also be present in the transition states and play a relevant role in the branching rations of the studied reactions. The reliability of Quantum Chemistry to predict and reproduce the kinetics of oxygenated VOCs reactions, as well as its capability to explain unusual experimental findings, is discussed.