Signatures of a bilayer structure in the photoelectron spectrum of B$_{80}^-$

Abstract

Recent photoelectron spectroscopy of B$_{80}^-$ was interpreted in terms of a fullerene-like cage structure. During our systematic investigation of medium-sized boron clusters, we identified a $D_{3h}$-symmetric bilayer isomer whose simulated photoelectron spectrum reproduces the principal features of the experimental photoelectron spectrum within 0.04 eV. The bilayer is energetically competitive with previously proposed structures and remains dynamically stable up to 1400 K according to ab initio molecular dynamics and vibrational analyses. Its electronic structure exhibits a 0.72 eV HOMO-LUMO gap and strong interlayer aromaticity, reflected by a NICS(0) value of $-44.3$ ppm in the interlayer B-B bonding region. These findings reveal a stable bilayer motif in the B$_{80}$ energy landscape and support its viability as a possible alternative structural assignment for the experimentally observed B$_{80}^-$.