Electronic structures and electronic spectra of all-boron fullerene B40

Abstract

This study is motivated by the recent discovery of the first all-boron fullerene analogue, a B₄₀ cluster with D_2d point-group symmetry, dubbed borospherene (Nat. Chem., 2014, 6, 727). Insight into the electronic structures and spectral properties of B₄₀ is timely and important to understand the borospherene and the transition from open-ended plate or ribbon-like structures to a hollow-cage structure at B₄₀. Optimized geometries of borospherene B₄₀ for both the ground state and the first excited state allow us to compute spectral properties including UV-vis absorption, infrared (IR) and Raman spectra. Highly resolved absorption and emission spectra are obtained, for the first time, for the fullerene at the time-dependent density-functional theory (TD-DFT) level within the Franck–Condon approximation and including the Herzberg–Teller effect. Assigned vibrational modes in absorption and emission spectra are readily compared with future spectroscopy measurements to distinguish the hollow-cage structure of D_2d-B₄₀ from other quasi-planar boron structures.