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1.
许洪光  吴苗苗  张增光  孙强  郑卫军 《中国物理 B》2011,20(4):43102-043102
Anion ion photoelectron spectroscopy and density functional theory (DFT) are used to investigate the electronic and structural properties of ScSin-(n=2~6) clusters and their neutrals. We find that the structures of ScSin- are similar to those of Sin+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 ScSi4,6- can be explained by the existence of less stable isomers. A comparison between ScSin- and VSin- clusters shows the effects of metal size and electron configuration on cluster geometries.  相似文献   

2.
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 SiN 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.  相似文献   

3.
The equilibrium geometries, relative stabilities, and electronic properties of Ca2Sin (n = 1-11) clusters have been systematically investigated by using the density function theory at the 6-311G (d) level The optimized geometries indicate that the most stable isomers have three-dimensional structures for n = 3-11. The electronic properties of Ca2 Sin (n = 1-11) dusters axe obtained through the analysis of the natural charge population, natural electron configuration, vertical ionization potential, and vertical electron affinity. The results show that the charges in corresponding Ca2Sin clusters transfer from the Ca atoms to the Sin host. Based on the obtained lowest-energy geometries, the size dependence of cluster properties, such as averaged binding energies, fragmentation energies, second-order energy differences, HOMO- LUMO gaps and chemical hardness, are deeply discussed.  相似文献   

4.
Gold-doped palladium clusters, Au2Pdn (n=1~4), are investigated using the density functional method B3LYP with relativistic effective core potentials (RECP) and LANL2DZ basis set. The possible geometrical configurations with their electronic states are determined, and the stability trend is investigated. Several low-lying isomers are determined, and many of them are in electronic configurations with a high-spin multiplicity. Our results indicate that the palladium-gold interaction is strong enough to modify the known pattern of bare palladium clusters, and the lower stability as the structures grow in size. The present calculations are useful to understanding the enhanced catalytic activity and selectivity gained by using gold-doped palladium catalyst.  相似文献   

5.
The first-principles method based on density-functional theory is used to investigate the geometries of the lowest-lying isomers of AunAg2 (n = 1 - 4) clusters. Several low-lying isomers are determined, and many of them in electronic configurations with a high spin multiplicity. The stability trend of Ag-doped Aun dusters is compared to that of pure Aun clusters. Our results indicate that the inclusion of two Ag atoms in the clusters lowers the cluster stability, indicating higher stability as the structures grow in size. The bigger energy difference between the Aun and AunAg2 curves as the structures grows in size. This information will be useful to understanding the enhanced catalytic activity and selectivity gained by using silver-doped gold catalyst.  相似文献   

6.
This paper computationally investigates the RhSin (n = 1 6) clusters by using a density functional approach. Geometry optimizations of the RhSin (n = 1 6) clusters are carried out at the B3LYP level employing LanL2DZ basis sets. It presents and discusses the equilibrium geometries of the RhSin (n = 1-6) clusters as well as the corresponding averaged binding energies, fragmentation energies, natural populations, magnetic properties, and the energy gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital. Theoretical results show that the most stable RhSin(n = 1-6) isomers keep an analogous framework of the corresponding Sin+1 clusters, the RhSi3 is the most stable cluster in RhSin (n = 1-6) isomers. Furthermore, the charges of the lowest-energy RhSin (n = 1-6) clusters transfer mainly from Si atom to Rh atom. Meanwhile, the magnetic moments of the RhSin(n = 1-6) arises from the 4d orbits of Rh atom. Finally, compared with the Sin+1 cluster, the chemical stability RhSin clusters are universally improved.  相似文献   

7.
Absorption spectra for Sn clusters (n=2...8) are calculated using an adiabatic time-dependent density functional formalism within the local density approximation (LDA). We compare the calculated spectra with those computed using a simple LDA approach. The time-dependent LDA (TDLDA) spectra display a significant blue shift with respect to the LDA spectra. The calculated spectra present a variety of features that can be used for comparison with future experimental investigations. We also obtain a significant threshold absorption, which can distinguish between different ground states of the sulfur clusters. In addition, the polarizabilities of the clusters are calculated by using the higherorder finite-difference pseudopotential density functional method in real space. We find that the polarizabilities of the clusters considered are higher than the value estimated from the 'hard sphere' model using the bulk static dielectric constant. The computed polarizabilities per atom tend to decrease with increasing cluster size. The polarizabilities are closely related to the HOMO-LUMO gaps and the geometrical configurations.  相似文献   

8.
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 Mg2Ni6 clusters 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.  相似文献   

9.
The hybrid density functional theory B3LYP with basis sets 6-31G* has been used to study on the equilibrium geometries and electronic structures of possible isomers of Si3N4 clusters. 24 possible isomers are obtained. The most stable isomer of Si3N4 is a 3D structure with 7 Si-N bonds and 2 N-N bonds that could beformed by 3 quadrangles. The bond properties of the most stable isomer was analyzed by using natural bond orbital method (NBO), the results suggest that the charges on Si and N atoms in Si-N bonds are quite large, so theinteraction of N-Si atoms in Si3N4 cluster is of strongly electric interaction. The primary IR and Raman vibrational frequency located at 1033.40 cm^-1, 473.63 cm^-1 respectively. The polarizabilities and hyperpolarizabilities of the most stable isomer are also analyzed.  相似文献   

10.
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.  相似文献   

11.
A parallel study on (BN)n and (HAlNH)n (n = 11-22) clusters is presented herein with ab initio HF/6-31G^* method. Two types of structures, i.e. cage-like and needle-shaped, are constructed. The calculated results indicate that the classical cage-like geometry is energetically more favourable for (BN)n while the needle-shaped (HAlNH)n structures are more stable than their cage-like counterparts. It is suggested that the nanostructures with higher structural similarity to the corresponding bulk phases possess greater stability. This idea leads to the viable way to intercept segment from bulk materials to construct models for theoretical study of complex nanostructures.  相似文献   

12.
13.
The full-core plus correlation method with multi-configuration interaction wave functions is extended to the calcu- lation of the non-relativistic energies of ls2nd (n ≤9) states for the lithium isoelectronic sequence from Z = 11 to 20. Relativistic and mass-polarization effects on the energy are calculated as the first-order perturbation correction. The quantum-electrodynamics correction is also included. The fine structure splittings are determined from the expectation values of spin-orbit and spin-other-orbit interaction operators in the Pauli-Breit approximation. Combining the term energies of lowly excited states obtained with the quantum defects calculated by the single channel quantum defect theory, each of which is a smooth function of energy and approximated by a weakly varying function of energy, the ion potentials of highly excited states (n ≥ 6) are obtained with the semi-empirical iteration method. The results are compared with experimental data in the literature and found to be closely consistent with the regularity.  相似文献   

14.
For the n+235U fission reaction, the total excitation energy partition of the fission fragments, the average neutron kinetic energy <ε>(A) and the total average energies Eγ(A) removed by γ rays as a function of fission fragment mass are given at incident energies up to 20 MeV. The prompt neutron multiplicity as a function of the fragment mass, ν(A), for neutron-induced fission of 235U at different incident neutron energies is calculated. The calculated results are checked with the total average prompt neutron multiplicities ν and compared with the experimental and evaluated data. Some prompt neutron and γ emission mechanisms are discussed.  相似文献   

15.
刘晶晶 《中国物理 C》2010,34(11):1700-1703
According to a new electron screening theory,we discuss the beta decay rates of nuclide 56Fe,56Co,56Ni,56Mn,56Cr and 56V with and without strong electron screening (SES).The results show that SES has only a slight effect on the beta decay rates for ρ/μe 108 g/cm3.However the beta decay rates would be influenced greatly for ρ/μe 108 g/cm3.Due to SES,the maximum values of the C-factor (in %) on beta decay rates of 56Fe,56Co,56Ni,56Mn,56Cr and 56V is of the order of 95.03%,35.02%,98.05%,80.33%,98.30% and 98.71% at T9 = 4.0 and 98.83%,98.89%,99.65%,10.32%,4.10% and 40.21% at T9 = 7.0,respectively.  相似文献   

16.
17.
Using the first-principles plane-wave pseudopotential method, based on the density function theory, the electron structure and optical properties of GaAs (100) β2(2×4) and GaAs (100) (4×2) reconstructions are calculated. The formation energy of As-richβ2 (2 ×4) reconstruction is minus and the formation energy of Ga-rich (4×2) reconstruction is positive; As-rich β2(2×4) reconstruction is stable and Ga-rich (4×2) reconstruction is unstable. Ga-rich (4×2) reconstruction owns lower work function. The electrons at two reconstructions both move into the bulk and form a band-binding region. Both the absorption and the refleetivity of As-rich β2(2×4) reconstruction are smaller than the Ga-rich (4× 2) reconstruction. As- rich β2(2×4) reconstruction is more benefit for the movement of photos through the surface to emit photoelectrons.  相似文献   

18.
利用原位红外光谱研究标题化合物在N2中的反应行为。发现它们在不同温度下能使乙酸分别转化为丙酮和甲烷。它们对乙酸的丙酮化反应活性顺序:[V3OAT]>[VFe2OAT],[V2CrOAT]>[Fe3OAT],[VCr2OAT]>[Cr3OAT][OAT=(μ3-O)(μ-O2CCH3)6(THF)3]。它们对乙酸的甲烷化反应活性顺序:[Cr3OAT]>[VCr2OAT],[V2CrOAT]>[V3OAT]>[VFe2OAT],[FeO3OAT]。对乙酸的丙酮化反应活性[Fe3OAT]明显低于[Fe3OAH][OAH=(μ3-O)(μ-O2CCH3)6(H2O)3]。对乙酸的甲烷化反应活性[Cr3OAT]也明显低于[CrOAH]。并对上述[Fe3OAT],[Cr3OAT]与[Fe3OAH],[Cr3OAH]之间差异进行了讨论  相似文献   

19.
Orbital responses to methyl sites in CnH2n+2 (n=1-6) are studied by B3LYP/TZVP based on the most stable geometries using the B3LYP/aug-cc-pVTZ method.Vertical ionization energies are produced using the SAOP/et-pVQZ model for the complete valence space.The highest occupied molecular orbital (HOMO) investigations indicate the pelectron profiles in methane,ethane,propane,and n-butane.By increasing the number of carbon-carbon bonds in lower momentum regions,the s,p-hybridized orbitals are built and display strong exchange and correlation interactions in lower momentum space (P<0.50 a.u.).Meanwhile,the relative intensities of the isomers in lower momentum space show the strong bonding number dependence of the carbon-carbon bonds,meaning that more electrons have contributed to orbital construction.The study of representative valence orbital momentum distribution further confirms that the structural changes lead to evident electronic rearrangement over the whole valence space.An analysis based on the isomers reveals that the valence orbitals are isomer-dependent and the valence ionization energy experiences an apparent shift in the inner valence space.However,such shifts are greatly reduced in the outer valence space.Meanwhile,the opposite energy shift trend is found in the intermediate valence space.  相似文献   

20.
伍冬兰  谢安东  万慧军  阮文 《物理学报》2011,60(10):176-181
采用不同方法B3P86,B3LYP,MP2和LSDA,结合Dunning的相关一致基组cc-PVTZ,对聚合型硼氢化物(BH3)n(n=1—3)分子的可能几何构型进行优化计算,得出最稳定构型的几何参数、电子结构、振动频率和光谱等性质参数,并给出了最稳定结构的总能量(ET),结合能(EBT),平均结合能(Eav),电离势(EIP),能隙(Eg),费米能级(EF)等.结果表明:采用密度泛函DFT中的方法B3P86计算的能量最低,结构参数更接近文献值;三种硼氢化物分子基态都为1重态,电子态分别为1A',1A和1A;BH3分子的最稳定几何构型为平面三角形结构;B2H6为对称性乙烯式D2h立体结构,H—B之间生成氢桥式三中心双电子键;B3H9为C3ν立体结构,也生成氢桥式三中心双电子键,但三个氢桥三中心双电子键彼此隔离.最后分析了三种氢化物的红外和拉曼光谱、平均结合能、电离势、能隙和费米能级等特性,说明(BH3)n(n=1—3)三分子中B2H6最稳定,H—B桥键键长比端键更长,最强峰红外光谱强度最大.  相似文献   

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