Factors Impacting σ- and π-Hole Regions as Revealed by the Electrostatic Potential and Its Source Function Reconstruction: The Case of 4,4′-Bipyridine Derivatives

Positive electrostatic potential (V) values are often associated with σ- and π-holes, regions of lower electron density which can interact with electron-rich sites to form noncovalent interactions. Factors impacting σ- and π-holes may thus be monitored in terms of the shape and values of the resulting V. Further precious insights into such factors are obtained through a rigorous decomposition of the V values in atomic or atomic group contributions, a task here achieved by extending the Bader–Gatti source function (SF) for the electron density to V. In this article, this general methodology is applied to a series of 4,4′-bipyridine derivatives containing atoms from Groups VI (S, Se) and VII (Cl, Br), and the pentafluorophenyl group acting as a π-hole. As these molecules are characterized by a certain degree of conformational freedom due to the possibility of rotation around the two C–Ch bonds, from two to four conformational motifs could be identified for each structure through conformational search. On this basis, the impact of chemical and conformational features on σ- and π-hole regions could be systematically evaluated by computing the V values on electron density isosurfaces (VS) and by comparing and dissecting in atomic/atomic group contributions the VS maxima (VS,max) values calculated for different molecular patterns. The results of this study confirm that both chemical and conformational features may seriously impact σ- and π-hole regions and provide a clear analysis and a rationale of why and how this influence is realized. Hence, the proposed methodology might offer precious clues for designing changes in the σ- and π-hole regions, aimed at affecting their potential involvement in noncovalent interactions in a desired way.

Identifying group contributions in NBA lineups with spectral analysis

We address the question of how to quantify the contributions of groups of players to team success. Our approach is based on spectral analysis, a technique from algebraic signal processing, which has several appealing features. First, our analysis decomposes the team success signal into components that are naturally understood as the contributions of player groups of a given size: individuals, pairs, triples, fours, and full five-player lineups. Secondly, the decomposition is orthogonal so that contributions of a player group can be thought of as pure: Contributions attributed to a group of three, for example, have been separated from the lower-order contributions of constituent pairs and individuals. We present detailed a spectral analysis using NBA play-by-play data and show how this can be a practical tool in understanding lineup composition and utilization.

Critical Constants Correlation from van der Waals Equation

The cubic van der Waals equation of state at the critical condition is reduced to a linear function (Vc vs. Tc /Pc coordinates) with one adjustable parameter. It is shown that at the critical point the relation Vc = 3Vo must not hold as van der Waals suggested, but the attractive constant α = Pc Vc2 remains. Selected values of Tc, Pc, Vc compiled by Ihmels where focused on testing the quality of several empirical equations relating critical conditions. It is shown that the obtained critical constants correlation is a general form of the empirical expressions proposed by Young, Meissner, Bird, Grigoras and Ihmels. From the resulting correlation function, a function for the critical compressibility is proposed. The critical volume Vc and the ratio Tc /Pc have been expressed in group contributions.