We study the surface crystalline and electronic structures of the antiferromagnetic topological insulator MnBi2Te4 using scanning tunneling microscopy/spectroscopy (STM/S), micro(μ)-laser angle-resolved photoemission spectroscopy (ARPES), and density functional theory calculations. Our STM images reveal native point defects at the surface that we identify as BiTe antisites and MnBi substitutions. Bulk X-ray diffraction further evidences the presence of the Mn-Bi intermixing. Overall, our characterizations suggest that the defects concentration is nonuniform within crystals and differs from sample to sample. Consistently, the ARPES and STS experiments reveal that the Dirac point gap of the topological surface state is different for different samples and sample cleavages, respectively. Our calculations show that the antiparallel alignment of the MnBi moments with respect to those of the Mn layer can indeed cause a strong reduction of the Dirac point gap size. The present study provides important insights into a highly debated issue of the MnBi2Te4 Dirac point gap.

Radical cyclization is among the most powerful and versatile reactions for constructing mono- and polycyclic systems, but has, to date, remained unexplored in the context of on-surface synthesis. We report the controlled on-surface synthesis of stable corrole radicals on Ag(111) via site-specific dehydrogenation of a pyrrole N-H bond in the 5,10,15-tris(pentafluoro-phenyl)-corrole triggered by annealing at 330 K under ultrahigh-vacuum conditions. We reveal a thermally induced regioselective cyclization reaction mediated by a radical cascade and resolve the reaction mechanism of the pertaining cyclodefluorination reaction at the single-molecule level. Via intramolecularly resolved probing of the radical-related Kondo signature, we achieve real space visualization of the distribution of the unpaired electron density over specific sites within the corrole radical. Annealing to 550 K initiates intermolecular coupling reactions, producing an extended π-conjugated corrole system.

Corrole compounds attract increasing interest due to their potential to stabilize high-valent metal states. X-ray spectroscopy is a powerful tool for the investigation and development of functional interfaces. For corrolic species, however, the required reference data are missing. Here, we employ a multitechnique X-ray investigation of thin films of the prototypical free-base 5,10,15-tris­(pentafluorophenyl)­corrole (3H-TpFPC) grown on the Ag(111) surface under ultrahigh vacuum conditions. Ultrapure corrole multilayer samples are prepared and characterized by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In parallel, the X-ray fingerprints are simulated using the continued-fraction approach within density functional theory (DFT) for extended, (quasi-)­periodic molecular structures. An excellent agreement between experimental and theoretical spectra enables a thorough interpretation of the detailed spectral features and proves an accurate description of the free-base corrole electronic structure within the present DFT approach. The present study provides X-ray spectroscopic references for all relevant core-level regions and absorption edges of intact molecular species and, thus, represents an ideal starting point for the comprehensive understanding of the complex chemistry of corroles in the adsorbed state toward the development of related functional interfaces.

We have determined the electron–phonon interaction in type II Dirac semimetallic 1T-PdTe2 by means of helium atom scattering. While 1T-PdTe2 is isostructural with 1T-PtTe2, only the former is superconductor. The difference can be traced to the substantially larger value of the electron–phonon coupling in 1T-PdTe2, λ = 0.58, obtained from the Debye-Waller attenuation of the He specular peak. With this value and the surface Debye temperature, ΘD = 106.2 K, we have figured out the superconducting critical temperature, Tc = 1.83 K given by the BCS theory, which is in good agreement with Tc = (1.95 ± 0.03) K obtained with low-temperature scanning tunneling microscopy. The value of the effective mass related to ΘD indicates that the large electron–phonon coupling in 1T-PdTe2 is due to coupling, not only with the zone-center optical mode O2 at 9.2 meV, as proposed in a recent theoretical study, but also with the zone-boundary acoustic mode LA. Our results suggest that the topological states of a Dirac cone play a negligible role on the onset of superconductivity.