Search

The geometries, electronic structures and related properties of SimN8-m(0 < m < 8) clusters are studied using density functional theory (DFT) with hybrid functional B3LYP. The calculated results reveal several trends. For any stoichiometric clusters, the lowest energy isomers with an alteration of N and Si atoms are favourable in energy if the numbers of Si and N atoms are large enough to form ... Si–N–Si–N... alternative chains. The bond lengths of single Si–N bonds are very close to the corresponding values of the bulk and other Si–N clusters. The geometries for N-rich and Si4N4 clusters are planar structures, but three-dimensional structures are favourable in energy for Si-rich clusters. With the increase of m, the isotropic polarizability and average polarizability increase, the total binding energies generally decrease, the HOMO-LUMO gap and vertical ionization potential oscillate with increasing number of valence electrons, and their values with even valence electrons are larger than those with odd valence electrons. The atomic charges, IR and Raman properties are also reported.

In this paper, possible structures of Ga5P5 cluster were optimized by using density functional method with generalized gradient correction (B3LYP). The electronic structure of the isomers with lower energy was studied. The most stable structure obtained for Ga5P5 is a distorted pentaprism. The Ga-P bond formed in the cluster is strongly ionic. Based on NBO analysis, an average value of 0.59 electron transfers from Gallium to Phosphorus. The bond length 2.33–2.43 A is around the value in bulk GaP. The HOMO-LUMO gap is about 2.2 eV. The dipole moment and polarizability are calculated, and the IR and Raman spectra are also presented.

The entropy and enthalpy changes upon absorption determine the equilibrium adsorption states, the adsorption/desorption kinetics, and the surface reaction rates. However, it is difficult to measure experimentally or calculate theoretically the entropy of adsorption state. Hydrogen is considered as the most promising candidate to solve the global energy problems, and the storage by adsorption on light porous solids constitutes a main avenue to research field. An ideal storage system should be able to operate under ambient conditions with high recycling capacity and suitable uptake-release kinetics. The entropy of adsorbed H2 molecules is of great significance for determining the optimum conditions for hydrogen storage and for designing the storage materials. To the best of our knowledge, however, the only report on the entropy of the adsorbed H2 molecules is that adsorbed on alkali-metal exchanged zeolites at temperatures around 100 K. Due to different assumptions of the entropy changes, the values of the optimum enthalpy H reported in the publications cover a wide range. In this paper, the adsorption states, vibrational modes, and the entropies of H2 molecules adsorbed on (MgO)9 and (AlN)12 clusters are studied by using first principal method. The computation is performed by the second-order perturbation theory (MP2) with the triple zeta basis set including polarization functions 6-311G(d, p). The very-tight convergence criterion is used to obtain reliable vibration frequencies. Analysis shows that six vibrational modes of the adsorption complexes can be attributed to the vibration of H2 molecule. For these normal modes, the amplitudes of the displacements of cluster atoms are usually two orders smaller than those of the hydrogen atoms. As the vibrational frequency is inversely proportional to the square root of the mass, the zero-point energy has an important influence on the adsorption energy. The ZPE correction exceeds half of the adsorption energy, and the adsorption on the anions is not stable after including the correction. Under the harmonic approximation, the normal vibration modes are independent, so the entropy of adsorbed H2 molecules can be calculated by using the vibrational partition function based on the vibrational frequencies. The results indicate that the entropy values depend mainly on the two lowest in-phase vibrational frequencies and it is not directly related to the adsorption strength but determined by the shape of the potential energy surface. In a temperature range of 70350 K and at a pressure of 0.1 MPa, there is a good linear correlation between the entropy of adsorbed H2 and the entropy of gas-phase. The entropy of H2 decreases about 10.2R after adsorption.

Hydrogen is considered as a potentially ideal substitution for fossil fuels in the future sustainable energy system because it is an abundant, clean and renewable energy carrier. A safe, efficient and economic storage method is the crucial prerequistite and the biggest challenge for the wide scale use of hydrogen. The nanomaterial is one of the most promising hydrogen storage materials because of its high surface to volume ratio, unique electronic structure and novel chemical and physical properties. It has been demonstrated that pristine nanostructures are not suitable for hydrogen storage, since they interact weakly with hydrogen molecule and their hydrogen storage density is very low. However, the hydrogen storage capacity of the nanostructures can be significantly enhanced through substitutional doping or decoration by metal atoms. Using density functional theory, we investigate the properties of hydrogen adsorption on Li-decorated C24clusters. Results show that the preferred binding site for Li atom is the pentagonal rings. The interaction of Li atoms with the clusters is stronger than that among Li atoms, thus hindering effectively aggregation of Li atoms on the surface of the cluster. The decorated Li atoms are positively charged due to electron transfer from Li to C atoms. When H2 molecules approach Li atoms, they are moderately polarized under the electric field, and adsorbed around the Li atoms in molecular form. Each Li atom in the Li-decorated C24 complexes can adsorb two to three H2 molecules. The H-H bond lengths of the adsorbed H2 molecules are slightly stretched. The average adsorption energies are in the range of 0.08 to 0.13 eV/H2, which are intermediate between physisorption and chemisorption. C24Li6 can hold up to 12 H2 molecules, corresponding to a hydrogen uptake density of 6.8 wt%. This value exceeds the 2020 hydrogen storage target of 5.5 wt% proposed by the U. S. Department of Energy.

With the accurate ab initio method, the adsorption and dissociation process of H2 molecule on Al7- cluster anion are investigated. The stable structures of molecular adsorption and dissociative adsorption are confirmed. The photoelectron spectra of different structures are further analyzed. The calculations indicate that the adsorption of H2 on Al7- is weak physical adsorption with the adsorption energy about 0.02 eV. The investigation of the dissociation process shows that the energy barrier of dissociation is about 0.75 eV. The densities of states of the Al7- cluster and the dissociative adsorption complex Al7H2- are in good agreement with those obtained by the photoelectron spectroscopy. It suggests that H2 can be dissociated when it is absorbed on Al7- anions produced by laser ablation.