Two-Dimensional Fluorinated Boron Sheets: Mechanical, Electronic, and Thermal Properties.

The synthesis of atomically thin boron sheets on a silver substrate opened a new area in the field of two-dimensional systems. Similar to hydrogenated and halogenated graphene, the uniform coating of borophene with fluorine atoms can lead to new derivatives of borophene with novel properties. In this respect, we explore the possible structures of fluorinated borophene for varying levels of coverage (B n F) by using first-principles methods. Following the structural optimizations, phonon spectrum analysis and ab initio molecular dynamics simulations are performed to reveal the stability of the obtained structures. Our results indicate that while fully fluorinated borophene (BF) cannot be obtained, stable configurations with lower coverage levels (B4F and B2F) can be attained. Unveiling the stable structures, we explore the mechanical, electronic, and thermal properties of (B n F). Fluorination significantly alters the mechanical properties of the system, and remarkable results, including direction-dependent variation of Young's modulus and a switch from a negative to positive Poisson's ratio, are obtained. However, the metallic character is preserved for low coverage levels, and metal to semiconductor transition is obtained for B2F. The heat capacity at a low temperature increases with an increasing F atom amount but converges to the same limiting value at high temperatures. The enhanced stability and unique properties of fluorinated borophene make it a promising material for various high-technology applications in reduced dimensions.

The interaction of halogen atoms and molecules with borophene.

The realization of buckled monolayer sheets of boron (i.e., borophene) and its other polymorphs has attracted significant interest in the field of two-dimensional systems. Motivated by borophene's tendency to donate electrons, we analyzed the interaction of single halogen atoms (F, Cl, Br, I) with borophene. The possible adsorption sites are tested and the top of the boron atom is found as the ground state configuration. The nature of bonding and strong chemical interaction is revealed by using projected density of states and charge difference analysis. The migration of single halogen atoms on the surface of borophene is analyzed and high diffusion barriers that decrease with atomic size are obtained. The metallicity of borophene is preserved upon adsorption but anisotropy in electrical conductivity is altered. The variation of adsorption and formation energy, interatomic distance, charge transfer, diffusion barriers, and bonding character with the type of halogen atom are explored and trends are revealed. Lastly, the adsorption of halogen molecules (F2, Cl2, Br2, I2), including the possibility of dissociation, is studied. The obtained results are not only substantial for fundamental understanding of halogenated derivatives of borophene, but also are useful for near future technological applications.

Effect of van der Waals interactions on the chemisorption and physisorption of phenol and phenoxy on metal surfaces.

The adsorption of phenol and phenoxy on the (111) surface of Au and Pt has been investigated by density functional theory calculations with the conventional PBE functional and three different non-local van der Waals (vdW) exchange and correlation functionals. It is found that both phenol and phenoxy on Au(111) are physisorbed. In contrast, phenol on Pt(111) presents an adsorption energy profile with a stable chemisorption state and a weakly metastable physisorbed precursor. While the use of vdW functionals is essential to determine the correct binding energy of both chemisorption and physisorption states, the relative stability and existence of an energy barrier between them depend on the semi-local approximations in the functionals. The first dissociation mechanism of phenol, yielding phenoxy and atomic hydrogen, has been also investigated, and the reaction and activation energies of the resulting phenoxy on the flat surfaces of Au and Pt were discussed.

Hyperbranched unsaturated polyphosphates as a protective matrix for long-term photon upconversion in air.

The energy stored in the triplet states of organic molecules, capable of energy transfer via an emissive process (phosphorescence) or a nonemissive process (triplet-triplet transfer), is actively dissipated in the presence of molecular oxygen. The reason is that photoexcited singlet oxygen is highly reactive, so the photoactive molecules in the system are quickly oxidized. Oxidation leads to further loss of efficiency and various undesirable side effects. In this work we have developed a structurally diverse library of hyperbranched unsaturated poly(phosphoester)s that allow efficient scavenging of singlet oxygen, but do not react with molecular oxygen in the ground state, i.e., triplet state. The triplet-triplet annihilation photon upconversion was chosen as a highly oxygen-sensitive process as proof for a long-term protection against singlet oxygen quenching, with comparable efficiencies of the photon upconversion under ambient conditions as in an oxygen-free environment in several unsaturated polyphosphates. The experimental results are further correlated to NMR spectroscopy and theoretical calculations evidencing the importance of the phosphate center. These results open a technological window toward efficient solar cells but also for sustainable solar upconversion devices, harvesting a broad-band sunlight excitation spectrum.

Ab initio characterization of graphene nanoribbons and their polymer precursors.

Bottom-up fabrication of graphene nanoribbons (GNRs) from halogen-terminated aromatic precursors is a promising method for achieving atomically precise nanoribbons at competitive yields. GNR fabrication proceeds via the polymerization of the precursors and successive dehydrogenation. By first principles density functional theory calculations, we perform a systematic characterization of the polymeric precursors and the corresponding graphene nanoribbons in terms of structural and electronic properties, and we compute the Raman and infrared spectra. The band structure properties are examined by considering the bonding features and the partial charge densities of the structures. The physical origin of the infrared and Raman peaks is investigated in terms of the morphology and vibrational properties of the precursors and products. We show that light spectroscopy provides a unique fingerprint for each type of GNR, which may be used to monitor the quality of the final products and the kinetics of the synthesis process.

Li+ and Li interactions with carbon nanocage structures.

Molecular dynamics simulations have been carried out to explore the structural properties of Li and Li+ confined inside single-walled carbon nanotubes (SWCNTs) and fullerene molecules. C-Li, C-Li+, Li-Li and Li+-Li+ interactions have been represented by pair functions and parameterized for the corresponding interactions. C-C interactions have been modeled by Tersoff potential. Open-ended SWCNTs with various sizes and chirality, as well as fullerenes with various sizes have been considered in the simulations. C-Li interaction is stronger than that of C-Li+. Endohedral Li+ doping caused structural deformations in C60. It has been found that for both Li and Li+ cases endohedral doping is favorable with respect to exohedral doping. This result is valid for both fullerenes and nanotubes.