Search

Fluorination of graphene sheets with xenon difluoride leads to the formation of the widest bandgap Gr derivative, namely, fluorographene. Accurate experimental observations distinguish two stages of mechanism in the fluorination procedure: the half-fluorination stage, wherein one side of the Gr sheet is rapidly fluorinated, and the full-fluorination stage, involving much slower fluorination of the opposite side of the sheet [R. J. Kashtiban et al., Nat. Commun. 5, 5902 (2014)]. Here, we perform comprehensive density functional calculations to illustrate accurate microscopic insights into the much slower rate of the full-fluorination stage compared with the half-fluorination one. The calculated minimum energy paths for the half- and full-fluorination processes demonstrate much enhanced fluorine adsorption after the half-fluorination stage, which sounds inconsistent with the experimental picture. This ambiguity is explained in terms of significant chemical activation of the graphene sheet after half-fluorination, which remarkably facilitates the formation of chemical contaminants in the system and, thus, substantially slows down the full-fluorination procedure. After considering the binding energy and durability of the relevant chemical species, including hydrogen, oxygen, and nitrogen molecules and xenon atom, it is argued that oxygen–fluorine ligands are the most likely chemical contaminants opposing the complete fluorination of a graphene sheet. Then, we propose an oxygen desorption mechanism to carefully explain the much enhanced rate of the full-fluorination procedure at elevated temperatures. The potential photocatalytic application of the pristine and defected samples in water splitting and carbon dioxide reduction reactions is also discussed. [ABSTRACT FROM AUTHOR]

In this study, we perform a systematic search to find the possible lowest energy structure of silicon nanoclusters Sin (n = 8-80) by means of an evolutionary algorithm. The fitness function for this search is the total energy of density functional tight binding (DFTB). To be on firm ground, we take several low energy structures of DFTB and perform further geometrical optimization by density functional theory (DFT). Then we choose structures with the lowest DFT total energy and compare them with the reported lowest energy structures in the literature. In our search, we found several lowest energy structures that were previously unreported. We further observe a geometrical transition at n = 27 from elongated to globular structures. In addition, the optical gap of the lowest energy structures is investigated by time-dependent DFTB (TD-DFTB) and time-dependent DFT (TD-DFT). The results show the same trend in TD-DFTB and TD-DFT for the optical gap. We also find a sudden drop in the optical gap at n = 27, precisely where the geometrical transition occurs. [ABSTRACT FROM AUTHOR]

In this paper, we employ an evolutionary algorithm along with the full-potential density functional theory (DFT) computations to perform a comprehensive search for the stable structures of stoichiometric (WS2)n nano-clusters (n = 1 - 9), within three different exchange-correlation functionals. Our results suggest that n = 5 and 8 are possible candidates for the low temperature magic sizes of WS2 nano-clusters while at temperatures above 500 Kelvin, n = 7 exhibits a comparable relative stability with n = 8. The electronic properties and energy gap of the lowest energy isomers were computed within several schemes, including semilocal Perdew-Burke-Ernzerhof and Becke- Lee-Yang-Parr functionals, hybrid B3LYP functional, many body based DFT+GW approach, ΔSCF method, and time dependent DFT calculations. Vibrational spectra of the lowest lying isomers, computed by the force constant method, are used to address IR spectra and thermal free energy of the clusters. Time dependent density functional calculation in a real time domain is applied to determine the full absorption spectra and optical gap of the lowest energy isomers of the WS2 nano-clusters. [ABSTRACT FROM AUTHOR]