Determination of sulfoxide bond dissociation enthalpies of dibenzothiophene S‐oxide derivatives with computational methods

Photodeoxygenation of dibenzothiophene S‐oxide (DBTO) has been suggested as a clean way to generate atomic oxygen in solution. Sulfoxide bond dissociation enthalpies (BDEs) are important to the quantum yield and mechanism of this photodeoxygenation. In this study, BDE of substituted DBTO molecules with various functional groups were determined using M062X/aug‐cc‐pV(T + d)Z and MP2/aug‐cc‐pV(T + d)Z levels of theory. The sulfoxide BDE was determined using an isodesmic reaction. The observed effect of substitution was that functional groups with negative σ_para values (electron donating) strengthen the sulfoxide bond and that substituents with positive σ_para values (electron withdrawing) weaken the sulfoxide bond. The Mulliken charge on sulfur for DBTO and the corresponding dibenzothiophene were identified as a suitable indicator of the predicted S–O BDE. Moreover, steric and hydrogen bonding interactions were found to affect sulfoxide BDE for certain functional groups when located at the 1 or 4 positions of the substituted DBTO. Copyright © 2014 John Wiley & Sons, Ltd.     

An upper limit to the cross section for the reaction νμe−→νμe− at SPS energies

Candidates for the purely leptonic process $\text{ν}{}_{\mathrm{\mu }}\text{e}{}^{\mathrm{?}}\text{→}\text{ν}{}_{\mathrm{\mu }}\text{e}{}^{\mathrm{?}}$ have been searched for in the bubble chamber Gargamelle exposed to the CERN-SPS antineutrino wide-band beam. No single e^?, of energy greater than 1 GeV, was found in a total of 230 000 pictures, corresponding to 7400 charged current events. This leads to an upper limit for the observed cross section of $\text{σ}{}_{\mathrm{<mtext>obs</mtext>}}\text{< 1.6 × 10}{}^{\mathrm{?42}}\text{(}\text{E}{}_{\mathrm{\nu }}{}^{\mathrm{?}}\text{GeV}\text{)}$ cm² (90% C.L.). Interpretation of this value in terms of the standard W Weinberg-Salam model yields an upper limit to the mixing parameter sin²θ_W < 0.39 at 90% C.L.     

Determination of loads applied perpendicularly to the outer boundary of a ring using coefficients of influence

A procedure is explained to determined the amount of several pairs of diametrical loads applied to the outside boundary of a ring when stresses at selected points of the inside or outside boundaries are known. Coefficients of influence are used, following an approach similar to the one presented in a previous paper. Examples of application are given and the possible increase in precision is shown when the number of points of measurements is larger than the number of loads to be determined.     

The MIDI! basis set for quantum mechanical calculations of molecular geometries and partial charges

We present a series of calculations designed to identify an economical basis set for geometry optimizations and partial charge calculations on medium-size molecules, including neutrals, cations, and anions, with special emphasis on functional groups that are important for biomolecules and drug design. A new combination of valence basis functions and polarization functions, called the MIDI! basis set, is identified as a good compromise of speed and accuracy, yielding excellent geometries and charge balances at a cost that is as affordable as possible for large molecules. The basis set is optimized for molecules containing H, C, N, O, F, P, S, and Cl. Although much smaller than the popular 6-31G* basis set, in direct comparisons it yields more accurate geometries and charges as judged by comparison to MP2/cc-pVDZ calculations.