π-Hole Tetrel Bonds—Lewis Acid Properties of Metallylenes

The MP2/aug-cc-pVTZ calculations were performed on the dihalometallylenes to indicate their Lewis acid and Lewis base sites. The results of the Cambridge Structural Database search show corresponding and related crystal structures where the tetrel center often possesses the configuration of a trigonal bipyramid or octahedron. The calculations were also carried out on dimers of dichlorogermylene and dibromogermylene and on complexes of these germylenes with one and two 1,4-dioxide molecules. The Ge⋯Cl, Ge⋯Br, and Ge⋯O interactions are analyzed. The Ge⋯O interactions in the above mentioned germylene complexes may be classified as the π-hole tetrel bonds. The MP2 calculations are supported by the results of the Quantum Theory of Atoms in Molecules (QTAIM) and the Natural Bond Orbital (NBO) approaches.

A Critical Review of Works Pertinent to the Einstein-Bohr Debate and Bell’s Theorem

This review is related to the Einstein-Bohr debate and to Einstein–Podolsky–Rosen’s (EPR) and Bohm’s (EPRB) Gedanken-experiments as well as their realization in actual experiments. I examine a significant number of papers, from my minority point of view and conclude that the well-known theorems of Bell and Clauser, Horne, Shimony and Holt (CHSH) deal with mathematical abstractions that have only a tenuous relation to quantum theory and the actual EPRB experiments. It is also shown that, therefore, Bell-CHSH cannot be used to assess the nature of quantum entanglement, nor can physical features of entanglement be used to prove Bell-CHSH. Their proofs are, among other factors, based on a statistical sampling argument that is invalid for general physical entities and processes and only applicable for finite “populations”; not for elements of physical reality that are linked, for example, to a time-like continuum. Bell-CHSH have, furthermore, neglected the subtleties of the theorem of Vorob’ev that includes their theorems as special cases. Vorob’ev found that certain combinatorial-topological cyclicities of classical random variables form a necessary and sufficient condition for the constraints that are now known as Bell-CHSH inequalities. These constraints, however, must not be linked to the observables of quantum theory nor to the actual EPRB experiments for a variety of reasons, including the existence of continuum-related variables and appropriate considerations of symmetry.

Indistinguishable elements in the origins of quantum statistics. The case of Fermi–Dirac statistics

In this paper, we deal with the historical origins of Fermi–Dirac statistics, focusing on the contribution by Enrico Fermi of 1926. We argue that this statistics, as opposed to that of Bose–Einstein, has been somewhat overlooked in the usual accounts of the old quantum theory. Our main objective is to offer a critical analysis of Fermi’s seminal paper and its immediate impact. Secondly, we are also interested in assessing the status of the particle concept in the years 1926–1927, especially regarding the germ of quantum indistinguishability. We will see, for example, that the first applications of the Fermi–Dirac statistics to the study of metals or stellar matter had a technical nature, and that their main instigators barely touched upon interpretative matters. Finally, we will discuss the reflections and remarks made in these respects in two famous events in physics of 1927, the Como conference and the fifth Solvay congress.

A novel hydrogen-bonding N-oxide–sulfonamide–nitro N—H...O synthon determining the architecture of benzenesulfonamide cocrystals

The structures of novel cocrystals of 4-nitropyridine N-oxide with benzenesulfonamide derivatives, namely, 4-nitrobenzenesulfonamide–4-nitropyridine N-oxide (1/1), C5H4N2O3·C6H6N2O4S, and 4-chlorobenzenesulfonamide–4-nitropyridine N-oxide (1/1), C6H6ClNO2S·C5H4N2O3, are stabilized by N—H...O hydrogen bonds, with the sulfonamide group acting as a proton donor. The O atoms of the N-oxide and nitro groups are acceptors in these interactions. The latter is a double acceptor of bifurcated hydrogen bonds. Previous studies on similar crystal structures indicated competition between these functional groups in the formation of hydrogen bonds, with the priority being for the N-oxide group. In contrast, the present X-ray studies indicate the existence of a hydrogen-bonding synthon including N—H...O(N-oxide) and N—H...O(nitro) bridges. We present here a more detailed analysis of the N-oxide–sulfonamide–nitro N—H...O ternary complex with quantum theory computations and the Quantum Theory of Atoms in Molecules (QTAIM) approach. Both interactions are present in the crystals, but the O atom of the N-oxide group is found to be a more effective proton acceptor in hydrogen bonds, with an interaction energy about twice that of the nitro-group O atoms.