Exhaustive exploration of the conformational landscape of mono- and disubstituted five-membered rings by DFT and MP2 calculations

The conformational landscape of 22 different non, mono-, and disubstituted compounds with a five-membered ring was thoroughly explored by ab initio (MP2) and DFT (B3LYP and M06-2X) methods with the 6-311+G** basis set.

Assignment of O–O and Mo=O Stretching Frequencies of Molybdenum/Tungsten Complexes Revisited

The assignment of peroxo stretching frequencies for Molybdenum and Tungsten complexes is studied by DFT and MP2 calculations. We found that M06 functional is unsuitable for assignment of Mo=O and O–O stretches in CpMo(η2-O2)OCH3and we found that MP2 and even the def2-TZVP do not give accurate order of asymmetric and symmetric Mo=O stretching. We recommend the M06L, which is a good compromise between speed and accuracy, for works involving these complexes. For a series of ten Molybdenum and Tungsten complexes studied we found that, for Mo/W=O stretching frequencies at M06L/def2-TZVP, after scaling, a small RMSD of 15 cm−1could be obtained. However peroxo stretching frequencies RMSD remains high at 40 cm−1after scaling. This could potentially point out the need for reassignment of experimental peroxo frequencies in some of the works cited in this report.

Amidinoquinoxaline N-oxides as novel spin traps

A series of nitrones were synthesized and tested as novel spin traps. The adducts generated by CH3 addition showed remarkably persistent signals. Their EPR features and kinetics were rationalised by DFT and MP2 calculations.

Experimental and theoretical studies on the photodegradation of 2-ethylhexyl 4-methoxycinnamate in the presence of reactive oxygen and chlorine species

Abstract2-Ethylhexyl 4-methoxycinnamate (EHMC) is one of the most commonly used sunscreen ingredient. In this study we investigated photodegradation of EHMC in the presence of such common oxidizing and chlorinating systems as H2O2, H2O2/HCl, H2O2/UV, and H2O2/HCl/UV. Reaction products were detected by gas chromatography with a mass spectrometric detector (GC-MS). As a result of experimental studies chloro-substituted 4-methoxycinnamic acid (4-MCA), 4-methoxybenzaldehyde (4-MBA) and 4-methoxyphenol (4-MP) were identified. Experimental studies were enriched with DFT and MP2 calculations. We found that reactions of 4-MCA, 4-MBA and 4-MP with Cl2 and HOCl were in all cases thermodynamically favorable. However, reactivity indices provide a better explanation of the formation of particular chloroorganic compounds. Generally, those isomeric forms of mono- and dichlorinated compounds which exhibits the highest hardness were identified. Nucleophilicity of the chloroorganic compounds precursors were examined by means of the Fukui function.