State-of-the-art electronic structure calculations (MR-CISD) are used to map five different dissociation channels of CH3Cl along the C-Cl coordinate: (i) CH3(X̃(2)A2″) + Cl((2)P), (ii) CH3(3s(2)A1') + Cl((2)P), (iii) CH3(+)((1)A1') + Cl(-)((1)S), (iv) CH3(3p(2)E') + Cl((2)P), and (v) CH3(3p(2)A2″) + Cl((2)P). By the first time these latter four dissociation channels, accessible upon VUV absorption, are described. The corresponding dissociation limits, obtained at the MR-CISD+Q level, are 3.70, 9.50, 10.08, 10.76, and 11.01 eV. The first channel can be accessed through nσ* and n3s states, while the second channel can be accessed through n(e)3s, n(e)3p(σ), and σ3s states. The third channel, corresponding to the CH3(+) + Cl(-) ion-pair, is accessed through n(e)3p(e) states. The fourth is accessed through n(e)3p(e), n(e)3p(σ), and σ3p(σ), while the fifth through σ3p(e) and σ(CH)σ* states. The population of the diverse channels is controlled by two geometrical spots, where intersections between multiple states allow a cascade of nonadiabatic events. The ion-pair dissociation occurs through formation of CH3(+)···Cl(-)and H2CH(+)···Cl(-) intermediate complexes bound by 3.69 and 4.65 eV. The enhanced stability of the H2CH(+)···Cl(-) complex is due to a CH···Cl hydrogen bond. A time-resolved spectroscopic setup is proposed to detect those complexes.

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The origin of the anomeric effect has remained an open question. After Mo demonstrated that hyperconjugation is not responsible for the anomeric effect [Y. Mo, Nature Chem., 2010, 2, 666.], electrostatic interactions and Pauli repulsions have been at the center of this debate. In this work, the total energies of the most stable rotamers of the equatorial and axial anomers of fluoro, hydroxyl, cyano and amino groups in cyclohexane and 2-substituted tetrahydropyran rings are decomposed into their fundamental kinetic, electrostatic and exchange components. In this partitioning scheme, the differences in the total energies among the most stable rotamers of each anomer correlate very well with the differences in the exchange components, revealing that the anomeric effect has no electrostatic origin. Indeed, the anomeric effect is dominated by the exchange energy. This proposal for the origin of the anomeric effect brings new insights that, once incorporated, may improve qualitative chemical models. Implications of this new proposal for the origin of the anomeric effect on geometric parameters and solvation are also discussed.

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Glyphosate (N-(phosphonomethyl)glycine) (Gph) is a herbicide that is broadly used in several countries. Its application to eliminate weeds may have the undesired effect of diminishing the metallic cations found in the soil (e.g., Ni(2+) and Zn(2+)), due to a complexation reaction that depends on the soil's pH. To better understand the molecular structures of glyphosate that are involved in such a complexation reaction, we have studied all possible glyphosate conformations in aqueous solution that may be involved in deprotonation reactions in the pH range from 2 to 11 using the polarizable continuum method (PCM). We have also compared direct (or absolute) methods to calculate pKa values, the cluster-continuum model and the proton-exchange scheme, using different thermodynamic cycles. The best result was achieved when using a proton-exchange scheme, which was able to properly reproduce three glyphosate experimental pKa values predicted for the glyphosate structures and conformations previously determined.

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The rate coefficients for the OH addition to 2-methyl-2-propen-1-ol and methylpropene have been determined, showing a non-Arrhenius profile and good agreement with the experimental data.