金团簇结构和电子性质的密度泛函研究

采用密度泛函理论,研究了Aun(2≤n≤10)团簇的最优结构和电子性质.采用各种不同的拓扑结构进行优化,计算结果显示最优结构都是二维的;在得到的最优结构基础上,进一步研究了其电子性质.结合能的二阶差分,费米能和能隙都显示了奇偶谐振效应.具有偶数个原子的金团簇要比奇数个原子的金团簇稳定,这与金团簇中的电子配对紧密相关.     

A density functional theory study of formaldehyde adsorption on ceria

Molecular adsorption of formaldehyde on the stoichiometric CeO₂(1 1 1) and CeO₂(1 1 0) surfaces was studied using periodic density functional theory. Two adsorption modes (strong chemisorbed and weak physisorbed) were identified on both surfaces. This is consistent with recent experimental observations. On the (1 1 1) surface, formaldehyde strongly chemisorbs with an adsorption energy of 0.86 eV to form a dioxymethylene-like structure, in which a surface O lifts from the surface to bind with the C of formaldehyde. A weak physisorbed state with adsorption energy of 0.28 eV was found with the O of formaldehyde interacting with a surface Ce. On the (1 1 0) surface, dioxymethyelene formation was also observed, with an adsorption energy of 1.31 eV. The weakly adsorbed state of formaldehyde on the (1 1 0) surface was energetically comparable to the weak adsorption state on the (1 1 1) surface. Analysis of the local density of states and charge density differences after adsorption shows that strong covalent bonding occurs between the C of formaldehyde and surface O when dioxymethylene forms. Calculated vibrational frequencies also confirm dioxymethylene formation. Our results show that as the coverage increases, the adsorption of formaldehyde on the (1 1 1) surface becomes weak, but is nearly unaffected on the (1 1 0) surface.     

The effect of a silica support: a density functional theory study of the C–H bond activation of ethane on a nickel oxide cluster

The support effect is an important issue in heterogeneous catalysis. A systematic density functional theory computational study is reported here to better understand the C–H bond activation steps in the reaction between C₂H₆ and a model silica‐supported Ni₃O₃ cluster, as well as that between C₂H₆ and an unsupported Ni₃O₃ cluster. Two mechanisms, namely, a radical mechanism (denoted as mechanism A) and a concerted mechanism (denoted as mechanism B) were examined. Both of these mechanisms contain two steps. For the C–H bond activation taking place via mechanism A, the involvement of the model silica support does not change the most favorable pathway significantly; however, it does result in a modest increase in the reaction barrier and the overall Gibbs energy change. For the C–H bond activation taking place via mechanism B, the involvement of the model silica support leads to an increase in the reaction barrier in the first step. The product of this step has a noticeable difference in the structures for the Ni₃O₃ moiety in the unsupported and model silica‐supported systems. The result of charge analysis shows that there is no noticeable charge transfer between the silica support and Ni₃O₃ when they are in the starting reactants, while there is an electron withdrawal from Ni₃O₃ by the silica support when they are in transition states, intermediates, or products. The results here provide deeper insights into the support effect on the C–H bond activation of lower alkanes on supported transition metal catalysts. Copyright © 2015 John Wiley & Sons, Ltd.     

Effects of the substrate on graphone magnetism: A density functional theory study

The magnetism of graphone, a single-side-hydrogenated graphene derivative, has been related to the localized and unpaired p-electrons associated with the unhydrogenated carbon atoms. In the present density functional theory study, the effects the adhesion to either Cu(111) or α-quartz (0001) surface on the magnetic properties of graphone have been investigated. The total magnetization of the graphone adsorbed to copper and quartz surface is reduced by four and two times, respectively, with respect to the isolated graphone. We have shown there is electronic charge transfer from surface towards three-fold coordinated C atoms of graphone, but the main role in the partial magnetism quenching is played by bond formation and the consequent electron pairing of p-electrons. The critical temperature has been investigated on the basis of the mean field theory to evaluate the stability of the magnetism at ordinary temperature.     

3d过渡金属原子单层在Pd(001)表面磁性的第一性原理研究

用第一性原理基础上的超软赝势方法的总能计算，研究了3d过渡金属(Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn)在Pd(001)表面的单层p(1×1)和c(2×2)结构的表面磁性和总能. 所得结果表明：对于Sc, Ti, V和Cr只存在p(1×1)的铁磁性结构，而Mn只有c(2×2)的反铁磁结构存在. Fe, Co和Ni这三种元素上述两种结构都存在，但是总能上p(1×1)的铁磁结构要低些，因此是比较稳定的结构. 而Cu和Zn在该表面上的单层中不存在上述两种结构. 对于V的p(1×1)铁磁结构，计算得到的每个V原子磁矩为2.41μ_B，大于用全电子方法得到的0.51μ_B. 两种计算方法得到其他金属原子 (Cr，Mn，Fe，Co，Ni)的表面磁矩比较相近，都比孤立原子磁矩略小. 关键词： Pd(001)表面 过渡金属原子单层 表面磁性     

Ca掺杂Si团簇的几何结构和电子性质的密度泛函理论研究

采用密度泛函理论(DFT)B3LYP方法在6-311+G(d,p)基组水平,对CaSi_n(n=1~10)的结构进行优化,得出各个尺寸下团簇处于最低能量的结构模型,并对其稳定性等物理化学性质进行理论研究,表明CaSi_2、CaSi_5和CaSi_9为幻数团簇.     

Band-gap engineering of La_(1-x)Nd_xAlO_3(x = 0,0.25,0.50,0.75,1)perovskite using density functional theory:A modified Becke Johnson potential study

The structural,electronic,and magnetic properties of the Nd-doped Rare earth aluminate,La_(1-x)Nd_xAlO_3(x = 0%to 100%) alloys are studied using the full potential linearized augmented plane wave(FP-LAPW) method within the density functional theory.The effects of the Nd substitution in La AlO_3 are studied using the supercell calculations.The computed electronic structure with the modified Becke–Johnson(m BJ) potential based approximation indicates that the La_(1-x)Nd_xAlO_3 alloys may possess half-metallic(HM) behaviors when doped with Nd of a finite density of states at the Fermi level(E_F).The direct and indirect band gaps are studied each as a function of x which is the concentration of Nddoped La AlO_3.The calculated magnetic moments in the La_(1-x)Nd_xAlO_3 alloys are found to arise mainly from the Nd-4f state.A probable half-metallic nature is suggested for each of these systems with supportive integral magnetic moments and highly spin-polarized electronic structures in these doped systems at E_F.The observed decrease of the band gap with the increase in the concentration of Nd doping in La AlO_3 is a suitable technique for harnessing useful spintronic and magnetic devices.     

A computational investigation of boron-doped chromium and chromium clusters by density functional theory

The geometries,stabilities and electronic properties of Crn and CrnB(n=2-9) clusters have been systematically investigated by density functional theory.The results suggest that the lowest energy structures for CrnB clusters can be obtained by substituting one Cr atom in Crn+1 clusters with B atom.The geometries of CrnB clusters are similar to that of Crn+1 clusters except for local structural distortion.The second-order difference and fragmentation energy show Cr4,Cr6,Cr8,Cr3B,Cr5B and Cr8B cluster are the ...     

Copper(I)‐catalyzed reaction of unsymmetrical alkyne with HB(pin): a density functional theory study

With the aid of density functional theory calculations, we have investigated the mechanism of copper(I)‐catalyzed reaction between unsymmetrical alkyne 1‐phenyl‐1‐butyne and HB(pin). The results of the density functional theory calculations show that the reaction mechanism involves syn‐addition of catalyst ([NHC]CuH) (NHC = N‐heterocyclic carbene) to 1‐phenyl‐1‐butyne to form the alkenyl copper intermediates 2a and 5a , and then intermediates 2a and 5a react with HB(pin) to give intermediates 3 ( 3a , 3b ) and 6 ( 6a , 6b ), and finally elimination of catalyst completes the catalytic cycle and yields the α‐product P₁ and β‐product P₂ . We found that α‐product should be more favored than β‐product. The calculated results are consistent with the experimental findings. The present paper may provide a useful guide for understanding other analogous copper‐catalyzed hydroboration of unsymmetrical alkynes.     

The cleavage of the methane CH bond over PdO/H-BEA: A density functional theory study

Cluster models were used to represent the β-type cationic sites of the protonated beta zeolite (H-BEA) and the loading of PdO on these sites. The properties of these clusters and the cleavage of methane CH bond over these clusters were studied using density functional theory (DFT) method. The stability of H-BEA was enhanced due to the formation of hydrogen bonds. After PdO loading, the Pd atom bonds to four oxygen atoms among which three H-BEA framework oxygen atoms are included to form an approximate planar structure with Pd in the centre. This structure is very similar to that of bulk PdO. The acidic proton of H-BEA and the oxygen atom of PdO participate in the cleavage of methane CH bond, indicating that PdO is the active species for the activation of methane. Over the clusters constructed in the present work, the calculated energy barriers for the cleavage of methane CH bond are in the region between 17.54 and 21.02 kcal mol⁻¹.     

Mechanism of ferromagnetism in(Fe,Co)-codoped 4H-SiC from density functional theory

First-principles calculations are performed to investigate the electronic structures and magnetic properties of(Fe, Co)-codoped 4H-SiC using the generalized gradient approximation plus Hubbard U method. We find that 4H-SiC doped with an isolated Fe atom and an isolated Co atom produces a total magnetic moment of 5.98 μ_B and 6.00 μ_B respectively. We estimate T_C of about 263.1 K for the(Fe, Co)-codoped 4H-SiC system. We study ferromagnetic and antiferromagnetic coupling in(Fe, Co)-codoped 4H-SiC. Ferromagnetic behavior is observed.The strong ferromagnetic couplings between local magnetic moments can be attributed to p–d hybridization between Fe, Co and neighboring C. However, the(Fe, Co, V_(Si))-codoped 4H-SiC system shows antiferromagnetic coupling when an Si vacancy is introduced in the same 4H-SiC supercell. The results may be helpful for further study on transition metal-codoped systems.     

Encapsulation of small fullerenes into nitrogenated holey nanotubes: a density functional theory study

Encapsulation of fullerene into nanotubes based on a C₂N sheet, known as nitrogenated holey graphene, was investigated using density functional theory. The structural and electronic properties of these carbon hybrid materials, consisting of nitrogenated holey nanotubes and a small C₂₀ fullerene, were studied. The formation energies showed that encapsulation of the fullerene into the nitrogenated holey nanotube is an exothermic process. To characterise the electronic properties, the electronic band structure and density of states of armchair and zigzag nitrogenated holey nanotubes were calculated. Filling these nanotubes with the C₂₀ fullerene resulted in a p-type semiconducting character. The energy band gap of the nitrogenated holey nanotubes decreased with fullerene encapsulation. The results are indicative of the possibility of band gap engineering by encapsulation of small fullerenes into nitrogenated holey nanotubes.     

Rhodium‐catalysed hydrogenation of enamides with monodentate phosphorous ligands. A density functional theory study

The hydrogenation of enamides catalysed by rhodium complexes of monodentate phosphorous ligands has been studied by density functional theory. The role of trans intermediates, made accessible by the non‐chelating nature of the ligand, has been taken into account. The findings here reported show that cis intermediates play the major role in the mechanism of the reaction, suggesting that data obtained with chiral monodentate phosphorous ligands or with a mixture of them should be interpreted excluding the intervention of structures with trans phosphine arrangement. Thus, results observed with monodentate phosphorous ligands must be interpreted in the light of the exclusive intervention of cis intermediates, without involvement of structures with trans phosphine arrangements. Copyright © 2010 John Wiley & Sons, Ltd.     

New ternary superconducting compound La Ru_2As_2:Physical properties from density functional theory calculations

In this paper, we perform the density functional theory(DFT)-based calculations by the first-principles pseudopotential method to investigate the physical properties of the newly discovered superconductor LaRu_2As_2 for the first time.The optimized structural parameters are in good agreement with the experimental results. The calculated independent elastic constants ensure the mechanical stability of the compound. The calculated Cauchy pressure, Pugh's ratio as well as Poisson's ratio indicate that LaRu_2As_2 should behave as a ductile material. Due to low Debye temperature, LaRu_2As_2 may be used as a thermal barrier coating(TBC) material. The new compound should exhibit metallic nature as its valence bands overlap considerably with the conduction bands. LaRu_2As_2 is expected to be a soft material and easily machinable because of its low hardness value of 6.8 GPa. The multi-band nature is observed in the calculated Fermi surface. A highly anisotropic combination of ionic, covalent and metallic interactions is expected to be in accordance with charge density calculation.     

Ammonia activation on platinum {1 1 1}: A density functional theory study

By means of density functional theory calculations we have investigated the role of adsorbed atomic oxygen and adsorbed OH in the oxidation of ammonia on Pt{1 1 1}. We have investigated the dissociation of NH_3,ads, NH_2,ads and NH_ads on Pt{1 1 1} and the oxidation of these species by O_ads and OH_ads. We have done normal mode frequency analysis and work function calculations to characterise reactant, product and transition states. We have determined reaction energies, activation entropies, kinetic parameters and corrected total energies with the zero point energy. We have shown that O_ads only activates the dehydrogenation of NH_3,ads and that OH_ads activates the dehydrogenation of all NH_x,ads species and have reasoned this difference in activation by a bond order conservation principle. We have pointed out the importance of a zero point energy correction to the reaction energies and barriers. We have compared the calculated vibrational modes of the adsorbates with corresponding experimental EELS data. This has led to a revise of the frequency assignment of ν(Pt-OH₂), a revise in the identification of a NH₂ species on the Pt{1 1 1} surface after electron bombardment of pre-adsorbed NH₃ and the confirmation of an ammonia dimer binding model at the expense of a hollow site occupation by ammonia on the Pt{1 1 1} surface.     

Basicity of neutral organic superbases with vinamidine structure in gas phase and acetonitrile: a density functional theory study

The gas‐phase proton affinities (PAs) for a set of molecules with vinamidine structure are considered and their basicities in acetonitrile. It is shown that introducing double bonds to the imidazoline rings at the proton attachment site resulted in decrease in PA of the parent vinamidine. The increase in PA can be obtained by inducing modifications to the imidazoline ring at the junction of two diazepinylium rings. Placing methyl and dimethylamino substituents on the perimeter of the molecule further increased their gas‐phase PAs. Studied vinamidine molecules are superbases, which possess PA values in the range between 261.0 and 284.2 kcal mol^–1 in the gas phase and pK_a values of 24.6–31.9 units in acetonitrile. Dismembering proton attachment site by opening the two diazepinylium and imidazoline rings resulted in the largest drop in PA values, indicating its importance in constraining the positions of imino nitrogen atoms in the neutral form of the molecule. Vinamidine molecules studied here present important pieces of the ladder of highly basic organic compounds for they possess accessible vinamidine molecular framework. Copyright © 2012 John Wiley & Sons, Ltd.     

Ferromagnetic properties of Cu-doped ZnS: A density functional theory study

Using plane-wave pseudopotential (PWPP) method, the magnetism and spin-resolved electronic properties of Cu-doped ZnS system are studied. Our calculations indicate that ferromagnetic (FM) state is ground state in Cu-doped ZnS. The FM coupling strength in ZnS doping with Cu fluctuates with the variation of distance between two dopants and the fluctuation gets larger with increase in distance. Room temperature ferromagnetism can be observed in Cu-doped ZnS with high dopant concentration. Formation energy calculation implies that the clustering effect is not obvious in Cu-doped ZnS. Thus, Cu-doped ZnS can be a promising dilute magnetic semiconductor (DMS), which promises to be free of magnetic precipitates.     

Understanding the role of Zn2+ in the hydrolysis of glycylserine: a mechanistic study by using density functional theory

The hydrolysis mechanism of glycylserine in the presence of Zn²⁺ was theoretically studied by means of density functional theory calculations. Two possible reaction mechanisms are proposed for the hydrolysis reaction: (1) the first one involves a stepwise reaction with an initial attack of the serine –OH to the amide carbonyl group through a general base catalysis of a water molecule, which undergoes to a proton transfer to the carboxylate group to give a cyclic intermediate. Its further rearrangement finally forms an ester that hydrolyses to yield products. (2) The second mechanism involves a general base catalysis by the carboxylate group for the water attack to the amide carbonyl group to generate a tetrahedral intermediate. Upon comparison of both mechanisms, it is observed that the former is favoured; furthermore, its first step is the rate-limiting step in a bicyclic asynchronous transition state with evolution of 86% in C₍₁₎–O₍₂₎ bond. The crucial role of Zn²⁺ in this hydrolysis process can be rationalised in terms of the inductive effect and the formation of a rigid structure that increases the electrophilicity of the amide carbonyl group. The calculations presented in this report are in good agreement with reported values for the activation barrier.