Photochemical reaction of the electronically excited NO(2)* species with the water molecule is studied in terms of a new version of density functional theory by selecting the specific (2)A'' symmetry of the whole system, which is different from the ground-state pattern. The excited C(2)A(2) state of the NO(2) molecule is found to be distorted to the equilibrium structure O=N-O(.), which poses the (2)A'' symmetry in the C(s) point group. With the B3LYP functional it is shown that such an electronically excited NO(2)* molecule, generated by visible light (λ=420 nm), can react with water vapor to produce OH+HONO species, an important source of tropospheric hydroxyl radicals. This photochemical process can be considered as a possible mechanism of atmosphere self-cleaning.

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The direct conversion of propane and butane fraction (existing as mixtures rather than separate products) to methanol as well as the reaction mechanism under visible light source (λ=420 nm) and the catalytic action of •NO2 have been evaluated. The purpose of this work is to explore novel pathways for the production of methanol by suggesting a simplified model and result-oriented scheme to avoid the drawbacks associated with methane activation (incredibly high activation energy of about 440 kJ/mol even under mild processing conditions) in the course of its transformation to methanol which is characterized by high yield and selectivity. It is important to consider propane and butane fraction (recovered from primary crude oil distillation and by cracking of heavy molecules) as a possible feedstock for methanol production exhibiting a sufficiently high degree of conversion per pass. Thereby, a relatively simple and economical method for methanol production from refined crude oil composed of propane and butane (a one step co-processing) have been tendered.