Density functional calculations on the geometric structure and properties of the 3d transition metal atom doped endohedral fullerene M@C20F20（M=Sc-Ni）

This paper uses the generalised gradient approximation based on density functional theory to analyse the geometric structure and properties of the 3d transition metal atom doped endohedral fullerene M@C20F20(M=Sc-Ni).The geometric optimization shows that the cage centre is the most stable position for M,forming the structure named as M@C 20 F 20-4.The inclusion energy,zero-point energy,and energy gap calculations tell us that Ni@C 20 F 20-4 should be thermodynamically and kinetically stablest.M@C 20 F 20-4(M = Sc-Co) possesses high magnetic moments varied from 1 to 6 μ B,while Ni@C 20 F 20-4 is nonmagnetic.The Ni-C bond in Ni@C 20 F 20-4 contains both the covalent and ionic characters.     

Density functional theory study of MgnNi2 （n=1-6） clusters

The geometries of Mg n Ni 2(n = 1-6) clusters are studied by using the hybrid density functional theory(B3LYP) with LANL2DZ basis sets.For the ground-state structures of Mg n Ni 2 clusters,the stabilities and the electronic properties are investigated.The results show that the groundstate structures and symmetries of Mg clusters change greatly due to the Ni atoms.The average binding energies have a growing tendency while the energy gaps have a declining tendency.In addition,the ionization energies exhibit an odd-even oscillation feature.We also conclude that n = 3,5 are the magic numbers of the Mg n Ni 2 clusters.The Mg 3 Ni 2 and Mg 5 Ni 2 clusters are more stable than neighbouring clusters,and the Mg 4 Ni 2 cluster exhibits a higher chemical activity.     

Density functional theory study of Mg_2Ni_n(n= 1–8) clusters

The density functional theory B3PW91 with LANL2DZ basis sets has been used to study the possible geometries of Mg2Nin(n = 1–8) clusters. For the lowest energy structures of the clusters, stabilities, electronic properties, and natural bond orbital(NBO) are calculated and discussed. The results show that the doped Mg atoms reduce the stabilities of pure Ni clusters. The Mg2Ni2, Mg2Ni4, and Mg2Ni6clusters are more stable than neighboring clusters. The system appears magic number characteristics. In addition, the hybridization phenomenon occurs, owing to the interaction of Mg and Ni. The result of charge transfer is that Ni atom is negative and the Mg atom is positive. We also conclude that the 3p and 4d orbitals of the Ni atom have an effect on the stabilities of the clusters.     

Stability of small Ni-Ti bimetallic clusters studied by density functional theory

The low-energy structures and the electronic and the magnetic properties of small NiNiNi$_{m}$Ti$_{n}$ clusters, lowest-energy structure, electronic and magnetic propertiesProject supported by the National Natural Science Foundation of China (Grant No.~10874039), and the Natural Science Foundation of Hebei Province of China (Grant Nos.~A2009000246 and 2009000243).3120A, 3640B, 2110K7/3/2009 12:00:00 AMThe low-energy structures and the electronic and the magnetic properties of small NiNiNi$_{m}$Ti$_{n}$ clusters, lowest-energy structure, electronic and magnetic propertiesProject supported by the National Natural Science Foundation of China (Grant No.~10874039), and the Natural Science Foundation of Hebei Province of China (Grant Nos.~A2009000246 and 2009000243).3120A, 3640B, 2110K7/3/2009 12:00:00 AMThe low-energy structures and the electronic and the magnetic properties of small Ni$_{n}$Ti$_{n}$ ($n=1$--$6$) and Ni$_{m}$Ti$_{n}$ ($1 \le n \le 4$, $1 \le m \le 4$, $n \ne m$) clusters are investigated by performing all-electron calculations based on density functional theory. Ground states and several isomers near the ground states are determined for these clusters. The results indicate that the growth of small Ni$_{m}$Ti$_{n}$ clusters prefers to form rich Ti--Ni and Ti--Ti bonds. When the percentage of titanium atoms is significantly greater than that of nickel atoms, the nickel atoms are most frequently found above the surface; in contrast, the titanium atoms prefer the bridging sites. A M\"{u}lliken spin population analysis indicates that the total spin of titanium-nickel clusters is not always zero.http://cpb.iphy.ac.cn/CN/10.1088/1674-1056/19/4/043102https://cpb.iphy.ac.cn/CN/article/downloadArticleFile.do?attachType=PDF&id=111644NimTin;clusters;lowest-energy;structure;electronic;and;magnetic;propertiesThe low-energy structures and the electronic and the magnetic properties of small Nin Tin(n = 1-6) and Ni m Ti n(1 ≤ n ≤ 4,1 ≤ m ≤ 4,n ≠ m) clusters are investigated by performing all-electron calculations based on density functional theory.Ground states and several isomers near the ground states are determined for these clusters.The results indicate that the growth of small Ni m Ti n clusters prefers to form rich Ti-Ni and Ti-Ti bonds.When the percentage of titanium atoms is significantly greater than that of nickel atoms,the nickel atoms are most frequently found above the surface;in contrast,the titanium atoms prefer the bridging sites.A Mu¨lliken spin population analysis indicates that the total spin of titanium-nickel clusters is not always zero.     

Structural, magnetic, electronic, and elastic properties of face-centered cubic PuHx （x=2, 3） ： GGA （LSDA） ＋ U ＋ SO

We perform first-principles calculations to investigate the structural, magnetic, electronic, and mechanical properties of face-centered cubic (fcc) PuH 2 and fcc PuH 3 using the full potential linearized augmented plane wave method (FP-LAPW) with the generalized gradient approximation (GGA) and the local spin density approximation (LSDA) taking account of both relativistic and strong correlation effects. The optimized lattice constant a0 = 5.371  for fcc PuH2 and a0 = 5.343  for fcc PuH3 calculated in the GGA + sp (spin polarization) + U (Hubbard parameter) + SO (spin-orbit coupling) scheme are in good agreement with the experimental data. The ground state of fcc PuH3 is found to be slightly ferromagnetic. Our results indicate that fcc PuH2 is a metal while fcc PuH3 is a semiconductor with a band gap about 0.35 eV. We note that the SO and the strong correlation between localized Pu 5f electrons are responsible for the band gap of fcc PuH3 . The bonds for PuH2 have mainly covalent character while there are covalent bonds in addition to apparent ionicity bonds for PuH3 . We also predict the elastic constants of fcc PuH2 and fcc PuH3 , which were not observed in the previous experiments.     

Structures and electronic properties of Mo2nNn（n=1-5）:a density functional study

The lowest-energy structures and the electronic properties of Mo2nNn(n=1-5) clusters have been studied by using the density functional theory(DFT) simulating package DMol 3 in the generalized gradient approximation(GGA).The resulting equilibrium geometries show that the lowest-energy structures are dominated by central cores which correspond to the ground states of Mo n(n = 2,4,6,8,10) clusters and nitrogen atoms which surround these cores.The average binding energy,the adiabatic electron affinity(AEA),the vertical electron affinity(VEA),the adiabatic ionization potential(AIP) and the vertical ionization potential(VIP) of Mo2nNn(n=1-5) clusters have been estimated.The HOMO-LUMO gaps reveal that the clusters have strong chemical activities.An analysis of Mulliken charge distribution shows that charge-transfer moves from Mo atoms to N atoms and increases with cluster size.     

First-principles study of disordering tendencies in Gd2B2O7（B=Ti,Sn,Zr） compounds

This paper performs the density functional theory calculations to obtain some factors influencing the response of pyrochlores Gd2B2O7(B = Ti,Sn,Zr) to ion irradiation-induced amorphization.The 48f oxygen position parameter x,cohesive energy,bond type and defect-formation energy are discussed.The results show that parameter x can be used to indicate the disordering tendencies within a given pyrochlore family.Bond type,cohesive energy and defect-formation energies can be used to explain some experimental observations,but they are not determined exclusively by radiation "resistance" for a different pyrochlore family.     

Density functional theory study of neutral AlS_n(n=2-9) clusters

This paper investigates the geometrical structures and relative stabilities of neutral AlS n(n = 2-9) using the density functional theory.Structural optimisation and frequency analysis are performed at the B3LYP/6-311G(d) level.The ground state structures of the AlS n show that the sulfur atoms prefer not only to evenly distribute on both sides of the aluminum atom but also to form stable structures in AlS n clusters.The structures of pure S n are fundamentally changed due to the doping of the Al atom.The fragmentation energies and the second-order energy differences are calculated and discussed.Among neutral AlS n(n = 2-9) clusters,AlS 4 and AlS 6 are the most stable.     

Structural and bonding properties of ScSi_n~-(n=2～6) clusters:photoelectron spectroscopy and density functional calculations

Anion ion photoelectron spectroscopy and density functional theory (DFT) are used to investigate the electronic and structural properties of ScSi_n^- (n=2sim6) clusters and their neutrals. We find that the structures of ScSi_n^- are similar to those of Si_n+1^-. The most stable isomers of ScSi_n^- cluster anions and their neutrals are similar for n=2, 3 and 5 but different for n=4 and 6, indicating that the charge effect on geometry is size dependent for small scandium-silicon clusters. The low electron binding energy (EBE) tails observed in the spectra of ScSi_4,6^- can be explained by the existence of less stable isomers. A comparison between ScSi_n^- and VSi_n^- clusters shows the effects of metal size and electron configuration on cluster geometries.     

First-principles study of mechanical stability and thermal properties of MNNi₃ （M=Zn,Mg,Al） under pressure

The mechanical stability,elastic,and thermodynamic properties of the anti-perovskite superconductors MNNi 3(M=Zn,Mg,Al) are investigated by means of the first-principles calculations.The calculated structural parameters and elastic properties of MNNi 3 are in good agreement with the experimental and the other theoretical results.From the elastic constants under high pressure,we predict that ZnNNi 3,MgNNi 3,and AlNNi 3 are not stable at the pressures above 61.2 GPa,113.3 GPa,and 122.4 GPa,respectively.By employing the Debye model,the thermodynamic properties,such as the heat capacity and the thermal expansion coefficient,under pressures and at finite temperatures are also obtained successfully.     

Ab initio study of structural,electronic and optical properties of ternary CdO1-xSex alloys using special quasi-random structures

The structural, electronic, and optical properties of binary CdO, CdSe, and their ternary CdO1 xSexalloys(0 ≤ x ≤ 1) in the rock salt and zinc blend phases have been studied by the special quasi-random structure(SQS) method. All the calculations are performed using full-potential linearized augmented plane wave plus local orbital’s(FP-LAPW+lo) method within the framework of density function theory(DFT). We use Wu–Cohen(WC) generalized gradient approximation(GGA) to calculate structural parameters, whereas both Wu–Cohen and Engel–Vosko(EV) GGA have been applied to calculate electronic structure of the materials. Our predicted results of lattice constant and bulk modulus show only a slight deviation from Vegard’s law for the whole concentrations. The obtained band structure indicates that for the rock-salt phase, the ternary alloys present semi-metallic behavior, while for the zinc blend phase, semiconductor behavior with direct bandgap is observed with decreasing order of x except for CdSe. Finally, by incorporating the basic optical properties, we discuss the dielectric function, refractive index, optical reflectivity, the absorption coefficient, and optical conductivity in terms of incident photon energy up to 14 eV. The calculated results of both binaries are in agreement with existing experimental and theoretical values.     

Static dipole polarizabilities of Scn （n ≤15） clusters

The static dipole polarizabilities of scandium clusters with up to 15 atoms are determined by using the numerically finite field method in the framework of density functional theory. The electronic effects on the polarizabilities are investigated for the scandium clusters. We examine a large highest occupied molecular orbital --- the lowest occupied molecular orbital (HOMO--LUMO) gap of a scandium cluster usually corresponds to a large dipole moment. The static polarizability per atom decreases slowly and exhibits local minimum with increasing cluster size. The polarizability anisotropy and the ratio of mean static polarizability to the HOMO--LUMO gap can also reflect the cluster stability. The polarizability of the scandium cluster is partially related to the HOMO--LUMO gap and is also dependent on geometrical characteristics. A strong correlation between the polarizability and ionization energy is observed.     

Role of Ga-doping in iron-gallium alloy clusters

The structural and magnetic properties of Fe_n-m Ga_m （n=3 ～ 6,m=0 ～ 2;n=13,m=0 ～ 3） alloy clusters have been studied using density functional theory.The substitutional doping is favourable for small clusters with up to six atoms at low Ga concentration and substitutional Ga atoms in 13-atom clusters prefer surface sites.The Ga-doping generally could reduce the energetic stability but enhance the electronic stability of Fe clusters,along with a decrease of the local magnetic moments of Fe atoms around Ga dopants.These findings provide a microscopic insight into Fe-Ga alloys which are well-known magnetostriction materials.     

A density functional theory study on size-dependent structures,stabilities,and electronic properties of bimetallic M_nAg_m(M=Na,Li;n + m≤7) clusters

The equilibrium geometries,relative stabilities,and electronic properties of Mn Agm(M=Na,Li;n + m ≤ 7) as well as pure Ag n,Na n,Li n(n ≤ 7) clusters are systematically investigated by means of the density functional theory.The optimized geometries reveal that for 2 ≤ n ≤ 7,there are significant similarities in geometry among pure Ag n,Na n,and Li n clusters,and the transitions from planar to three-dimensional configurations occur at n = 7,7,and 6,respectively.In contrast,the first three-dimensional(3D) structures are observed at n + m = 5 for both Na n Ag m and Li n Ag m clusters.When n + m ≥ 5,a striking feature is that the trigonal bipyramid becomes the main subunit of Li n Ag m.Furthermore,dramatic odd-even alternative behaviours are obtained in the fragmentation energies,secondorder difference energies,highest occupied and lowest unoccupied molecular orbital energy gaps,and chemical hardness for both pure and doped clusters.The analytic results exhibit that clusters with an even electronic configuration(2,4,6) possess the weakest chemical reactivity and more enhanced stability.     

The structural,electronic, and magnetic properties of SrFeOn（n=2 and 2.5）： a GGA＋U study

Using density-functional calculations within the generalized gradient approximation (GGA)+U framework,we investigate the structural,electronic,and magnetic properties of the ground states of SrFeOn (n = 2 and 2.5).The magnetism calculations show that the ground states of both SrFeO2 and SrFeO2.5 have G type antiferromagnetic ordering,with indirect band gaps of 0.89 and 0.79 eV,respectively.The electronic structure calculations demonstrate that Fe cations are in the high-spin state of (dz2 )2(dxz,dyz)2(dxy)1(dx2 y2 )1(S = 2),unlike the previous prediction of (dxz,dyz)3(dxy)1(dz2 )1(dx2 y2 )1(S = 2) for SrFeO2,and in the high-spin state of (dxy,dxz,dyz,dx2 y2 ,dz2 )5(S = 5/2) for SrFeO2.5.     

First-principles study of the electronic and optical properties of ZnO nanowires

The geometric, energetic, electronic structures and optical properties of ZnO nanowires (NWs) with hexagonal cross sections are investigated by using the first-principles calculation of plane wave ultra-soft pseudo-potential technology based on the density functional theory (DFT). The calculated results reveal that the initial Zn-O double layers merge into single layers after structural relaxations, the band gap and binding energies decrease with the increase of the ZnO nanowire size. Those properties show great dimension and size dependence. It is also found that the dielectric functions of ZnO NWs have different peaks with respect to light polarization, and the peaks of ZnO NWs exhibit a significant blueshift in comparison with those of bulk ZnO. Our results gives some reference to the thorough understanding of optical properties of ZnO, and also enables more precise monitoring and controlling during the growth of ZnO materials to be possible.     

Differences in the adsorption of FePc on coinage metal surfaces

A study of the electronic and structural properties of iron phthalocyanine(FePc) molecules adsorbed on coinage metal surfaces Cu(100) and Cu(110) has been conducted by means of density functional theory calculations.The strength of the molecule-substrate interactions is interpreted in terms of the lateral adsorption geometry and the site specific electronic structure of the molecule.In the case of FePc on a(100)-oriented copper surface,the benzopyrrole leg is found to be oriented at an angle of 9° or 3° from the [01-1] substrate direction.Further,an upward bend in the molecular plane ranging from 7° to 10° is also observed;giving an almost buckled shape to the molecule.However,in the case of FePc on Cu(110),neither a bend nor a sizable rotation is observed.From the knowledge of the principle structural and electronic properties,it is concluded that FePc-Cu(100) interaction is relatively stronger than FePc-Cu(110) interaction,which is further evidenced by the charge transfer,work function changes,changes in the shape of the adsorbed molecular orbitals,and the orbital shifts.Furthermore,density of states analysis shows that the valence band level shift is surface-and site-dependent.     

High stability of the goldalloy fullerenes:A density functional theory investigation of M₁₂@Au₂₀（M=Na,Al,Ag,Sc,Y,La,Lu,and Au） clusters

Discovering highly stable metal fullerenes such as the celebrated C 60 is interesting in cluster science as they have potential applications as building blocks in new nanostructures.We here investigated the structural and electronic properties of the fullerenes M 12 @Au 20(M=Na,Al,Ag,Sc,Y,La,Lu,and Au),using a first-principles investigation with the density functional theory.It is found that these compound clusters possess a similar cage structure to the icosahedral Au 32 fullerene.La 12 @Au 20 is found to be particularly stable among these clusters.The binding energy of La 12 @Au 20 is 3.43 eV per atom,1.05 eV larger than that in Au 32.The highest occupied molecular orbital-lowest unoccupied molecular orbital(HOMO-LUMO) gap of La 12 @Au 20 is only 0.31 eV,suggesting that it should be relatively chemically reactive.     

Electronic and optical properties of pure and Ce3+-doped CaS single crystals: a first-principles prediction

This paper investigates the electronic and optical properties for pure and Ce 3+-doped CaS crystals by using the first-principles total energy calculations.The results show that CaS:Ce has a direct band gap of 2.16 eV,and the top of the valence band is determined by S 3p states and the bottom of the conduction band is determined by Ce 4f states,respectively.Our results validate that the yellow emission from CaS:Ce is produced by doped cerium and the green emission quenches at 12.5% cerium concentration.The Ce-S bond shows more covalent character than the Ca-S bond.     

Density functional study of the pressure tensor for inhomogeneous Lennard—Jones fluids

Based on classical density functional theory,an expression of the pressure tensor for inhomogeneous fluids is presented.This takes into account greater correlation between particles,especially for systems that are geometrically confined or involve an interface.The density and pressure components of Lennard-Jones fluids confined in hard and softened nano-cavities are calculated.A comparison between the results of this work and IK expression suggests that the agreement depends on temperature.The interfacial tension for hard sphere fluids agrees well with the Monte Carlo result when the bulk density is not too large.The results of the solid-fluid interfacial tension for Lennard-Jones fluids demonstrate that different types of external potentials modulate the interfacial tension in different manners.