Ab Initio Calculations on Bismuth Cluster Polycations

Abstract

Ab initio calculations on bismuth polycationic species of the types Bi(n(n-2))+, Bi(n(n-4))+, and Bi(n(n-6))+ (n = 3 - 12) were performed at the Hartree-Fock and density functional theory levels in order to investigate their general properties and the applicability of Wade's rules on bismuth polycations. Some exceptions to Wade's rules were encountered, and, moreover, several predicted and calculated minima show only meta-stable behavior. The bonding in bismuth polycations is characterized by a high degree of electron delocalization and "three-dimensional aromaticity".

Ionothermal Syntheses, Crystal Structures, and Chemical Bonding of the Rhodium‐Centered Clusters [RhBi9]4+and [(RhBi7)I8]

“…Deviations from the experimental values of the average interatomic distances are within the accuracy interval of 10 pm found for true energy-minimum geometries of bismuth polycations. [27] These elongations can be explained by unaccounted crystal field effects in the calculations. Nevertheless, the effective QTAIM charges (Table S4, Table S7) are not too high to warrant a charge compensation scheme.…”

“…The emerging bonding situation in Bi 10 4+ with threecenter interactions in the triangular facets connecting the two pentagonal basal planes is in line with the description given earlier. [27] The resultant bonding picture [Pd 0 @Bi 10 4+ ] also accords with the earlier data obtained from the extended Hückel calculations. [2a] (Table S11, Supporting Information).…”

Group theoretical treatment of Jahn–Teller versus spin-orbit effects on geometries, rovibronic levels and nuclear spin species of bismuth and antimony clusters

“…Electronic structural and spectroscopic studies of group (15) clusters have been the focus of a number of studies [4][5][6][7][8][9][14][15][16][17] due to their interesting open-shell electronic features and as a consequence of the JahnTeller distortions, which have led to dynamic spectra arising from the pseudorotation. Clusters containing Bi atoms are particularly intriguing due to the interplay between relativistic effects and spin-orbit effects [12,15].…”

Reprint of “Coordination chemistry of homoatomic ligands of bismuth, selenium and tellurium”

“…Modifications of Wade's rules, which were originally developed for hydroboranes [21,22], help to understand the chemical bonding and to correlate electron count with shape [23]. Formal replacement of n B H exo-bonds by n Bi 6s lone-pairs also results in 2n + m skeletal electrons (SE), i.e.…”