Jahn–Teller instability in cationic boron and carbon buckyballs B80+ and C60+: a comparative study

Abstract

This paper investigates the Jahn-Teller effect in the icosahedral cation B(80)(+) and compares the descent in symmetry with that in C(60)(+). For both cations the icosahedral ground state is a (2)H(u) state, which exhibits a H ⊗ (g ⊕ 2h) Jahn-Teller instability. A detailed construction of the potential energy surface of B(80)(+) using different DFT methods including B3LYP/6-31G(d), VWN/6-31G(d), PBE/TZP and PBE/6-31G(d) shows that, contrary to C(60)(+), which prefers D(5d) symmetry, the ground state of B(80)(+) adopts S(6) point group symmetry. A D(3d) structure is identified as a saddle point among the S(6) minima of B(80)(+). The distortion of D(3d) to S(6) in B(80)(+) is attributed to a superposition of Jahn-Teller and pseudo-Jahn-Teller effects. Imaginary modes, transforming as the g(g) representation, which are present in neutral icosahedral B(80), form the dominant symmetry breaking active modes. The pronounced difference between the JT effects in the boron and carbon buckyball cations is due to the plasticity of the boron caps. The calculated Jahn-Teller stabilization of B(80)(+) is nearly 1549 cm(-1) (PBE/TZP), which exceeds the stabilization of 596 cm(-1) computed for C(60)(+) at the same level.

Probing the structure and electronic properties of beryllium doped boron clusters: A planar BeB16− cluster motif for metallo-borophene

“…Recently, systematic investigations of pure boron clusters in term of the anisotropy and polymorphism have brought forth new significant findings leading to the design of new borides. A selection of characteristic architectures of pure boron clusters includes: tank tread 34 , wankel motor 35–39 , wheel-like 40 , boron nanotubes 41 , B 12 icosahedra 42 , buckyballs 43 , fullerene 44 , B 36 with hexagonal holes (HHs) 45 , naphthalene 46 , borospherene 47 and more. Co and Rh doped B 12 − clusters featured half-sandwich structure has been reported by Wang and co-workers 48 .…”

A particle on a hollow cylinder: the triple ring tubular cluster B27+

“…In other cases, Jahn-Teller and pseudo-Jahn-Teller effects are also of primordial importance in the stabilization of boron clusters yielding lower symmetry structures. [13][14][15] Regarding the tubular forms of boron clusters, the neutral B 20 was found to be the first size having a double ring tube (DR) in which the two ten-membered rings are connected together in an antiprism bonding motif. [16][17][18] This DR was calculated to be a few kcal mol À1 more stable than the quasiplanar isomer.…”

Electronic Transitions Responsible for C60+ Diffuse Interstellar Bands

“…An electron ejection from the h u molecular orbital in icosahedral C 60 is followed by the Jahn–Teller distortion to the D 5 d isomer of C 60 + (Figure ). − The other possible distortions to D 2 h and D 3 d geometries lead to energetically unfavorable transition states and higher-order stationary points, respectively. In good agreement with previous studies, , our calculations indicate that the D 5 d isomer has no imaginary frequencies and stabilized by 976 cm –1 with respect to the icosahedral C 60 + .…”