Origins of Stability in Mixed Bismuth−Indium Clusters

Abstract

The electronic structure and stability of neutral and negatively charged Bi x In y (x ) 1-4, y ) 1-6) clusters are investigated through anionic photoelectron spectroscopy employing magnetic bottle and photoelectron velocity map imaging experiments. Experimental and theoretical adiabatic and vertical detachment energies of the anionic species containing up to 4 Bi and 4 In atoms are deduced from first principles calculations. Among the Bi x In y series, many clusters are found to exhibit special stability in the mass spectra, exhibit a large gap between the highest occupied and lowest unoccupied molecular orbitals (HOMO-LUMO gap), and a large formation energy. This stability is rationalized by different mechanisms. Bi 2 Inis classified as a gas phase Zintl species despite only having three atoms, making it the smallest possible case. Bi 3 In 2 -, with 12 valence electrons and a closo structure in agreement with Wade's rule, is similar to Bi 3 Ga 2 -, a gas phase Zintl analogue of Sn 5 2-. Bi 4 Inand Bi 4 In 2 are both found to follow Wade's rule, indicating gas phase Zintl clusters. BiIn 3 is a cyclic planar molecule similar to BiGa 3 and BiAl 3 , all-metal aromatic systems, and BiIn 5 is a 20 electron closed shell Jellium species. Additionally, an even-odd oscillation of the HOMO-LUMO gaps, formation energies, and adiabatic electron affinities are found correlating with the open-shell/closedshell nature of the clusters.

Novel Dilute Bismide, Epitaxy, Physical Properties and Device Application

“…Gupta et al did a series of work on the Bi containing neutral, ionic clusters such as In x Bi (x = 1-4) [88], BiGa y [89] and Bi x In y [90], using experimental results (photoelectron spectroscopy, velocity map imaging) and first principle theoretical methods. The results of structures, electronic energy levels, molecular orbitals and photoelectron spectra for all the Bi containing clusters are obtained.…”

“…[87] Bicluster [88][89][90][91] Bi doped GaAs NWs [94] Bi 4+ ions [98] Bi NWs, Nanotubes [87] Bi cluster [88][89][90][91] Bi-doped GaAs NWs [94] …”

Mimicking the magnetic properties of rare earth elements using superatoms

“…Moreover, to validate our calculated lowest-energy geometries of the anionic and neutral LaB clusters, the theoretical ADE and VDE of LaB − were computed to compare with the experimentally measured values. It is worth noting that such a comparison is particularly helpful in diagnosing the accuracy of the theoretically proposed structures and bonding mechanisms (27,30,31). The theoretical ADE and VDE values of the LaB − clusters are 0.947 and 0.957 eV, respectively, calculated at the CCSD(T) level of theory, and summarized in Table 2.…”

Photoelectron spectroscopy and density functional theory study of Bi2Aln− (n=1–4) clusters

“…For the Bi atoms, the LANL2DZ basis set [23] was used, in which the relativistic effective core potentials (RECPs) were incorporated. It has been shown that RECPs are common and efficient ways to reduce the complex calculations for molecules containing heavy atoms such as Bi [9,10,[24][25][26]. The geometry optimizations were conducted without any symmetry constraint.…”

“…In the last decades, the clusters consisting of III-V elements were investigated intensively by experiments [4][5][6][7][8][9][10] and theoretical calculations [11][12][13][14][15][16][17]. Neumark and co-workers [4][5][6] studied the size selected Al/P, Ga/P, In/P, and Ga/As cluster anions by photoelectron spectroscopy (PES).…”