Search for Global Minimum Structures of P2n+1+ (n = 1–15) Using xTB-Based Basin-Hopping Algorithm

A new program for searching global minimum structures of atomic clusters using basin-hopping algorithm based on the xTB method was developed here. The program can be performed with a much higher speed than its replacement directly based on DFT methods. Considering the structural varieties and complexities in finding their global minimum structures, phosphorus cluster cations were studied by the program. The global minimum structures of cationic P2n+1+ (n = 1–15) clusters are determined through the unbiased structure searching method. In the last step, further DFT optimization was performed for the selected isomers. For P2n+1+ (n = 1–4, 7), the found global minimum structures are in consistent with the ones previously reported; while for P2n+1+ (n = 5, 6, 8–12), newly found isomers are more energy-favorable than those previously reported. And those for P2n+1+ (n = 13–15) are reported here for the first time. Among them, the most stable isomers of P2n+1+ (n = 4–6, 9) are characterized by their C3v, Cs, C2v and Cs symmetry, in turn. But those of P2n+1+ (n = 7, 8, 10–12), no symmetry has been identified. The most stable isomers of P29+ and P31+ are characterized by single P-P bonds bridging units inside the clusters. Further analysis shows that the pnicogen bonds play an important role in the stabilization of these clusters. These results show that the new developed program is effective and robust in searching global minimum structures for atom clusters, and it also provides new insights into the role of pnicogen bonds in phosphorus clusters.

Competition and conversion between pnicogen bonds and hydrogen bonds involving prototype organophosphorus compounds

Ab initio calculations have been performed to investigate the competition and conversion between the pnicogen bonds and hydrogen bonds in the complexes containing prototype organophosphorus compounds RPO2 (R = CH3...

Hydrogen Bond and Other Lewis Acid–Lewis Base Interactions as Preliminary Stages of Chemical Reactions

Various Lewis acid–Lewis base interactions are discussed as initiating chemical reactions and processes. For example, the hydrogen bond is often a preliminary stage of the proton transfer process or the tetrel and pnicogen bonds lead sometimes to the SN2 reactions. There are numerous characteristics of interactions being first stages of reactions; one can observe a meaningful electron charge transfer from the Lewis base unit to the Lewis acid; such interactions possess at least partly covalent character, one can mention other features. The results of different methods and approaches that are applied in numerous studies to describe the character of interactions are presented here. These are, for example, the results of the Quantum Theory of Atoms in Molecules, of the decomposition of the energy of interaction or of the structure-correlation method.