Geometries and spectroscopic properties of germanium and tin hexamers (Ge6, Ge6+, Ge6−, Sn6, Sn6+, and Sn6−)

Abstract

Spectroscopic properties of novel aromatic metal clusters: NaM 4 ( M = Al,Ga,In ) and their cations and anionsGround and excited electronic states of neutral, cationic and anionic germanium and tin hexamers ͑Ge 6 and Sn 6 ͒ are investigated. Different geometries such as tetragonal bipyramid (D 4h ,D 2h ) and edge-caped trigonal bipyramid (C 2v ) ͑ECTBP͒ were studied. We have employed a number of high level electron correlation techniques such as large scale multireference singlesϩdoubles configuration interaction ͑MRSDCI͒ computations that included up to 16 million configurations, complete active-space multiconfiguration self-consistent filed ͑CAS-MCSCF͒, and Møller-Plesset ͑MP2͒ techniques to investigate the low-lying electronic states, their geometries and energy separations. A 1 A 1g tetragonal bipyramid structure ͑D 4h symmetry͒ is found as the ground state for both Ge 6 and Sn 6 , in accord with the previously suggested experimental assignments. The excitation energies, atomization energies, ionization potentials and vertical and adiabatic electron affinities are computed and compared with the experimental results. Our computations of the excited states of these species have facilitated assignment of the anion photodetachment spectra of the anions of these clusters and comparison with the photoionization spectra of the neutral species.

Density Functional Investigation of Structure and Stability of Gen and GenNi (n = 1−20) Clusters: Validity of the Electron Counting Rule

“…The planar rhombus is found to be 2.15 eV lower in energy than the T d structure. These are in general agreement with previous works. ,, …”

“…These again are in general agreement with previous studies. [10][11][12][13][14] As far as the Ge 8 cluster is concerned, three different stable structures are found. The ground-state Ge 8 (A) structure is obtained by adding one germanium atom above the plane of the capped hexagonal structure of Ge 7 (A).…”

“…In this age of nanotechnology, study of Si and Ge clusters has attracted a lot of theoretical and experimental attention due to their importance in the electronic industry. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] However, both pure Si and Ge clusters are chemically reactive. 18 Therefore one needs to stabilize them for any potential application.…”

Spectroscopic properties of novel aromatic metal clusters: NaM4 (M=Al,Ga,In) and their cations and anions

“…While multiply charged main group cluster anions have been known in aqueous solution, and they are also constituents of solids (zintl ions), it is unusual to find such multiply charged cluster ions in the gas-phase. Moreover these dianions are found to be planar aromatic [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] in contrast to other main group clusters [16][17][18][19][20][21][22][23] , which exhibit threedimensional structures.…”

“…Spectroscopy and theoretical studies of main group clusters have received considerable attention in the last two decades [16][17][18][19][20][21][22][23] as they exhibit interesting structures and properties that vary dramatically with cluster sizes. High-resolution spectroscopic studies of such clusters are on the increase due to the ready generation of these species in the gas-phase with the advent of supersonic jet expansion methods.…”