Geometries and electronic properties of the neutral and charged rare earth Yb-doped Si(n) (n = 1-6) clusters: a relativistic density functional investigation

The neutral and charged YbSi(n) (n = 1-6) clusters considering different spin configurations have been systematically investigated by using the relativistic density functional theory with generalized gradient approximation. The total bonding energies, equilibrium geometries, Mulliken populations (MP), Hirshfeld charges (HC), fragmentation energies, and highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps are calculated and discussed. The optimized geometries indicate that the most stable YbSi(n) (n = 1-6) clusters keep basically the analogous frameworks as the low-lying Si(n)(+1) clusters, while the charged species deviate from their neutral counterparts, and that the doped Yb tends to occupy the substitutional site of the neutral and charged YbSi(n) isomers. The relative stabilities are investigated in terms of the calculated fragmentation energies, exhibiting enhanced stabilities for the remarkably stable neutral and charged YbSi2 and YbSi5 clusters. Furthermore, the calculated MP and HC values show that the charges of the neutral and charged YbSi(n) clusters transfer from the Yb atom to Si(n) atoms and the Yb atom acts as an electron donor, and that the f orbitals of the Yb atom in the neutral and charged YbSi(n) clusters behave as core without involvement in chemical bonding. The calculated HOMO-LUMO gaps indicate that the YbSi2 and YbSi4+ clusters have stronger chemical stabilities. Comparisons of the Yb-doped Si(n) (n = 1-6) with available theoretical results of transition-metal-doped silicon clusters are made. The growth pattern is investigated also.     

Relativistic computational investigation: the geometries and electronic properties of TaSi(n)+ (n = 1-13, 16) clusters

The equilibrium geometries, stabilities, and electronic properties of the TaSi(n)+ (n = 1-13, 16) clusters are investigated systematically by using the relativistic density functional method with generalized gradient approximation. The small-sized TaSi(n)+ clusters with slight geometrical adjustments basically keep the frameworks that are analogous to the neutrals while the medium-sized charged clusters significantly deform the neutral geometries, which are confirmed by the calculated AIP and VIP values. Furthermore, the optimized geometries of the charged clusters agree with the experimental results of Hiura and co-workers (Hiura, H.; Miyazaki, T.; Kanayama, T. Phys. Rev. Lett. 2001, 86, 1733). The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) gaps of the charged clusters are generally increased as the cluster size goes from n = 1 to 13; and the large HOMO-LUMO gaps of charged clusters resulting from the positive charge indicate that their chemical stabilities are stronger than their neutral counterparts, especially for n = 4, 6, and 7 clusters. Additionally, the contributions of the d orbitals of the Ta atom to the HOMO and LUMO reveal that the chemical activity of the d orbitals of the Ta atom decreases gradually as the number of silicon atoms increases. This interesting finding is in good agreement with the recent experimental results on the reactive activities of the H2O and transition-metal silicon clusters (Koyasu, K.; Akutsu, M.; Mitsui, M.; Nakajima, A. J. Am. Chem. Soc. 2005, 127, 4998). Generally, the positive charge significantly influences the electronic and geometric structures of the charged clusters. Finally, the most stable neutral and charged TaSi16 clusters are found to be fullerene-like structures and the HOMO-LUMO gap in charged form is detectable experimentally.     

A density functional study of YnAl (n=1-14) clusters

The geometries, stabilities, and electronic and magnetic properties of Y(n)Al (n=1-14) clusters have been systematically investigated by using density functional theory with generalized gradient approximation. The growth pattern for different sized Y(n)Al (n=1-14) clusters is Al-substituted Y(n+1) clusters and it keeps the similar frameworks of the most stable Y(n+1) clusters except for Y(9)Al cluster. The Al atom substituted the surface atom of the Y(n+1) clusters for n<9. Starting from n=9, the Al atom completely falls into the center of the Y-frame. The Al atom substituted the center atom of the Y(n+1) clusters to form the Al-encapsulated Y(n) geometries for n>9. The calculated results manifest that doping of the Al atom contributes to strengthen the stabilities of the yttrium framework. In addition, the relative stability of Y(12)Al is the strongest among all different sized Y(n)Al clusters, which might stem from its highly symmetric geometry. Mulliken population analysis shows that the charges always transfer from Y atoms to Al atom in all different sized clusters. Doping of the Al atom decreases the average magnetic moments of most Y(n) clusters. Especially, the magnetic moment is completely quenched after doping Al in the Y(13), which is ascribed to the disappearance of the ininerant 4d electron spin exchange effect. Finally, the frontier orbitals properties of Y(n)Al are also discussed.     

Geometries, stabilities, and electronic properties of different-sized ZrSi(n) (n=1-16) clusters: a density-functional investigation

The ZrSi(n) (n=1-16) clusters with different spin configurations have been systematically investigated by using the density-functional approach. The total energies, equilibrium geometries, growth-pattern mechanisms, natural population analysis, etc., are discussed. The equilibrium structures of different-sized ZrSi(n) clusters can be determined by two evolution patterns. Theoretical results indicate that the most stable ZrSi(n) (n=1-7) geometries, except ZrSi3, keep the analogous frameworks as the lowest-energy or the second lowest-energy Si(n+1) clusters. However, for large ZrSi(n) (n=8-16) clusters, Zr atom obviously disturbs the framework of silicon clusters, and the localized position of the transition-metal (TM) Zr atom gradually varies from the surface insertion site to the concave site of the open silicon cage and to the encapsulated site of the sealed silicon cage. It should be mentioned that the lowest-energy sandwich-like ZrSi12 geometry is not a sealed structure and appears irregular as compared with other TM@Si12 (TM = Re,Ni). The growth patterns of ZrSi(n) (n=1-16) clusters are concerned showing the Zr-encapsulated structures as the favorable geometries. In addition, the calculated fragmentation energies of the ZrSi(n) (n=1-16) clusters manifest that the magic numbers of stabilities are 6, 8, 10, 14, and 16, and that the fullerene-like ZrSi16 is the most stable structure, which is in good agreement with the calculated atomic binding energies of ZrSi(n) (n=8-16) and with available experimental and theoretical results. Natural population analysis shows that the natural charge population of Zr atom in the most stable ZrSi(n) (n=1-16) structures exactly varies from positive to negative at the critical-sized ZrSi8 cluster; furthermore, the charge distribution around the Zr atom appears clearly covalent in character for the small- or middle-sized clusters and metallic in character for the large-sized clusters. Finally, the properties of frontier orbitals and polarizabilities of ZrSi(n) are also discussed.     

Structural and electronic properties of Si n, Si n+, and AlSi n-1 (n=2-13) clusters: theoretical investigation based on ab initio molecular orbital theory

The geometric and electronic structures of Si(n), Si(n) (+), and AlSi(n-1) clusters (2< or =n< or =13) have been investigated using the ab initio molecular orbital theory under the density functional theory formalism. The hybrid exchange-correlation energy function (B3LYP) and a standard split-valence basis set with polarization functions [6-31G(d)] were employed for this purpose. Relative stabilities of these clusters have been analyzed based on their binding energies, second difference in energy (Delta (2)E) and fragmentation behavior. The equilibrium geometry of the neutral and charged Si(n) clusters show similar structural growth. However, significant differences have been observed in the electronic structure leading to their different stability pattern. While for neutral clusters, the Si(10) is magic, the extra stability of the Si(11) (+) cluster over the Si(10) (+) and Si(12) (+) bears evidence for the magic behavior of the Si(11) (+) cluster, which is in excellent agreement with the recent experimental observations. Similarly for AlSi(n-1) clusters, which is isoelectronic with Si(n) (+) clusters show extra stability of the AlSi(10) cluster suggesting the influence of the electronic structures for different stabilities between neutral and charged clusters. The ground state geometries of the AlSi(n-1) clusters show that the impurity Al atom prefers to substitute for the Si atom, that has the highest coordination number in the host Si(n) cluster. The fragmentation behavior of all these clusters show that while small clusters prefers to evaporate monomer, the larger ones dissociate into two stable clusters of smaller size.     

Computational investigation of TiSin (n=2-15) clusters by the density-functional theory

The geometries, stabilities, and electronic properties of TiSin (n=2-15) clusters with different spin configurations have been systematically investigated by using density-functional theory approach at B3LYP/LanL2DZ level. According to the optimum TiSin clusters, the equilibrium site of Ti atom gradually moves from convex to surface, and to a concave site as the number of Si atom increases from 2 to 15. When n=12, the Ti atom in TiSi12 completely falls into the center of the Si outer frame, forming metal-encapsulated Si cages, which can be explained by using 16-electron rule. On the basis of the optimized geometries, various energetic properties are calculated for the most stable isomers of TiSin clusters, including the average binding energy, the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO-LUMO) gap, fragmentation energy, and the second-order difference of energy. It is found that at size n=6,8,12 the clusters are more stable than neighboring ones. According to the Mulliken charge population analysis, charges always transfer from Si atoms to Ti atom. Furthermore, the HOMO-LUMO gaps of the most stable TiSin clusters are usually smaller than those of Sin clusters.     

Geometries, stabilities, and growth patterns of the bimetal Mo2-doped Sin (n=9-16) clusters: a density functional investigation

The behaviors of the bimetal Mo-Mo doped cagelike silicon clusters Mo2Sin at the size of n=9-16 have been investigated systematically with the density functional approach. The growth-pattern behaviors, relative stabilities, and charge-transfer of these clusters are presented and discussed. The optimized geometries reveal that the dominant growth patterns of the bimetal Mo-Mo doped on opened cagelike silicon clusters (n=9-13) are based on pentagon prism MoSi10 and hexagonal prism MoSi12 clusters, while the Mo2 encapsulated Sin(n=14-16) frames are dominant growth behaviors for the large-sized clusters. The doped Mo2 dimer in the Sin frames is dissociated under the interactions of the Mo2 and Sin frames which are examined in term of the calculated Mo-Mo distance. The calculated fragmentation energies manifest that the remarkable local maximums of stable clusters are Mo2-doped Sin with n=10 and 12; the obtained relative stabilities exhibit that the Mo2-doped Si10 cluster is the most stable species in all different sized clusters. Natural population analysis shows that the charge-transfer phenomena appearing in the Mo2-doped Sin clusters are analogous to the single transition metal Re or W doped silicon clusters. In addition, the properties of frontier orbitals of Mo2-doped Sin (n=10 and 12) clusters show that the Mo2Si10 and Mo2Si12 isomers have enhanced chemical stabilities because of their larger HOMO-LUMO gaps. Interestingly, the geometry of the most stable Mo2Si9 cluster has the framework which is analogous to that of Ni2Ge9 cluster confirmed by recent experimental observation (Goicoechea, J. M.; Sevov, S. C. J. Am Chem. Soc. 2006, 128, 4155).     

Equilibrium geometries, stabilities, and electronic properties of the bimetallic M2-doped Au(n) (M = Ag, Cu; n = 1-10) clusters: comparison with pure gold clusters

The density functional method with relativistic effective core potential has been employed to investigate systematically the geometrical structures, relative stabilities, growth-pattern behaviors, and electronic properties of small bimetallic M(2)Au(n) (M = Ag, Cu; n = 1-10) and pure gold Au(n) (n ≤ 12) clusters. The optimized geometries reveal that M(2) substituted Au(n+2) clusters and one Au atom capped M(2)Au(n-1) structures are dominant growth patterns of the stable alloyed M(2)Au(n) clusters. The calculated averaged atomic binding energies, fragmentation energies, and the second-order difference of energies as a function of the cluster size exhibit a pronounced even-odd alternation phenomenon. The analytic results exhibit that the planar structure Ag(2)Au(4) and Cu(2)Au(2) isomers are the most stable geometries of Ag(2)Au(n) and Cu(2)Au(n) clusters, respectively. In addition, the HOMO-LUMO gaps, charge transfers, chemical hardnesses and polarizabilities have been analyzed and compared further.     

Density-functional study of structural and electronic properties of Si(n)C(n) (n=1-10) clusters

Density-functional theory with generalized gradient approximation for the exchange-correlation potential has been used to calculate the structural and electronic structure of Si(n)C(n) (n=1-10) clusters. The geometries are found to undergo a structural change from two dimensional to three dimensional when the cluster size n equals 4. Cagelike structures are favored as the cluster size increases. A distinct segregation between the silicon and carbon atoms is observed for these clusters. It is found that the C atoms favor to form five-membered rings as the cluster size n increases. However, the growth motif for Si atoms is not observed. The Si(n)C(n) clusters at n=2, 6, and 9 are found to possess relatively higher stability. On the basis of the lowest-energy geometries obtained, the size dependence of cluster properties such as binding energy, HOMO-LUMO gap, Mulliken charge, vibrational spectrum, and ionization potential has been computed and analyzed. The bonding characteristics of the clusters are discussed.     

Structural and electronic properties of Si(n), Si(n)-, and PSi(n-1) clusters (2 < or = n < or = 13): Theoretical investigation based on ab initio molecular orbital theory

The geometric and electronic structures of Si(n), Si(n)-, and PSi(n-1) clusters (2 < or = n < or = 13) have been investigated using the ab initio molecular orbital theory formalism. The hybrid exchange-correlation energy functional (B3LYP) and a standard split-valence basis set with polarization functions (6-31+G(d)) were employed to optimize geometrical configurations. The total energies of the lowest energy isomers thus obtained were recalculated at the MP2/aug-cc-pVTZ level of theory. Unlike positively charged clusters, which showed similar structural behavior as that of neutral clusters [Nigam et al., J. Chem. Phys. 121, 7756 (2004)], significant geometrical changes were observed between Si(n) and Si(n)- clusters for n = 6, 8, 11, and 13. However, the geometries of P substituted silicon clusters show similar growth as that of negatively charged Si(n) clusters with small local distortions. The relative stability as a function of cluster size has been verified based on their binding energies, second difference in energy (Delta2 E), and fragmentation behavior. In general, the average binding energy of Si(n)- clusters is found to be higher than that of Si(n) clusters. For isoelectronic PSi(n-1) clusters, it is found that although for small clusters (n < 4) substitution of P atom improves the binding energy of Si(n) clusters, for larger clusters (n > or = 4) the effect is opposite. The fragmentation behavior of these clusters reveals that while small clusters prefer to evaporate monomer, the larger ones dissociate into two stable clusters of smaller size. The adiabatic electron affinities of Si(n) clusters and vertical detachment energies of Si(n)- clusters were calculated and compared with available experimental results. Finally, a good agreement between experimental and our theoretical results suggests good prediction of the lowest energy isomeric structures for all clusters calculated in the present study.     

Geometries and stabilities of Ag-doped Si n (n=1-13) clusters: a first-principles study

The structures of AgSi(n) (n=1-13) clusters are investigated using first-principles calculations. Our studies suggest that AgSi(n) clusters with n=7 and 10 are relatively stable isomers and that these clusters prefer to be exohedral rather than endohedral. Moreover, doping leaves the inner core structure of the clusters largely intact. Additionally, the plot of fragmentation energies as a function of silicon atoms shows that the AgSi(n) are favored to dissociate into one Ag atom and Si(n) clusters. Alternative pathways exist for n>7 (except n=11) in which the Ag-Si cluster dissociates into a stable Si(7) and a smaller fragment AgSi(n-7). The AgSi(11) cluster dissociates into a stable Si(10) and a small fragment AgSi. Lastly, our analysis indicates that doping of Ag atom significantly decreases the gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital for n>7.     

TbSin(n=2-13)团簇的结构、电子及磁学性质

利用相对论密度泛函理论在广义梯度近似下研究TbSi_n (n=2-13)团簇的结构、稳定性、电子和磁学性质. 对团簇的平均结合能、离解能、电荷转移、最高占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)的能级差、Mulliken 电荷分析和磁学性质进行了计算和讨论. TbSi_n团簇并没有像实验推测的那样在n=10形成嵌入式的结构. 我们推断电子亲和势的急剧变化不仅与嵌入式的结构有关, 而且与电子的固有稳定性相关.Mulliken 电荷分析表明电荷总是从Tb 原子转向Si 原子. 团簇的磁矩主要局域在Tb 原子的周围, 并且主要由f电子贡献, f 电子表现出局域性并且不参与化学成键. 以TbSi₁₀为例的分波态密度分析表明Tb与Si 原子间存在很强的sp轨道杂化.     

A Gaussian-3 theoretical study of small silicon-lithium clusters: electronic structures and electron affinities of SinLi(-) (n = 2-8)

The molecular structures of neutral Si n Li ( n = 2-8) species and their anions have been studied by means of the higher level of the Gaussian-3 (G3) techniques. The lowest energy structures of these clusters have been reported. The ground-state structures of neutral clusters are "attaching structures", in which the Li atom is bound to Si n clusters. The ground-state geometries of anions, however, are "substitutional structures", which is derived from Si n+1 by replacing a Si atom with a Li (-). The electron affinities of Si n Li and Si n have been presented. The theoretical electron affinities of Si n are in good agreement with the experiment data. The reliable electron affinities of Si n Li are predicted to be 1.87 eV for Si 2Li, 2.06 eV for Si 3Li, 2.01 eV for Si 4Li, 2.61 eV for Si 5Li, 2.36 eV for Si 6Li, 2.21 eV for Si 7Li, and 3.18 eV for Si 8Li. The dissociation energies of Li atom from the lowest energy structures of Si n Li and Si atom from Si n clusters have also been estimated respectively to examine relative stabilities.     

A density-functional study of Al-doped Ti clusters: TinAl (n = 1-13)

Equilibrium geometries, stabilities, and electronic properties of TinAl (n = 1-13) clusters have been studied by using density-functional theory with local spin density approximation and generalized gradient approximation. The ground-state structures of TinAl clusters have been obtained. The resulting geometries show that the aluminum atom remains on the surface of clusters for n < 9, but is slowly getting trapped beyond n = 9, meanwhile, the Al atom exhibits a valent transition from monovalent to trivalent. The geometric effects and electronic effects clearly demonstrate the Ti4Al cluster to be endowed with special stability. The studies on the bonds indicate the change from ionic to metalliclike.     

Geometries and magnetisms of the Zr(n) (n=2-8) clusters: the density functional investigations

The geometries, stabilities, and electronic and magnetic properties of small-sized Zr(n) (n=2-8) clusters with different spin configurations were systematically investigated by using density functional approach. Emphasis is placed on studies that focus on the total energies, equilibrium geometries, growth-pattern behaviors, fragmentation energies, and magnetic characteristics of zirconium clusters. The optimized geometries show that the large-sized low-lying Zr(n) (n=5-8) clusters become three-dimensional structures. Particularly, the relative stabilities of Zr(n) clusters in terms of the calculated fragmentation energies and second-order difference of energies are discussed, exhibiting that the magic numbers of stabilities are n=2, 5, and 7 and that the pentagonal bipyramidal D(5h) Zr(7) geometry is the most stable isomer and a nonmagnetic ground state. Furthermore, the investigated magnetic moments confirm that the atomic averaged magnetic moments of the Zr(n) (n not equal to 2) display an odd-even oscillation features and the tetrahedron C(s) Zr(4) structure has the biggest atomic averaged magnetic moment of 1.5 mu(B)/at. In addition, the calculated highest occupied molecular orbital-lowest unoccupied molecular orbital gaps indicate that the Zr(n) (n=2 and 7) clusters have dramatically enhanced chemical stabilities.     

用密度泛函理论研究ZrnB(n=1-13)团簇的结构及性质

利用密度泛函理论, 得到了ZrnB(n=1-13)团簇的基态结构, 计算并讨论了团簇能量的二阶差分和离解能. 结果表明, n=2, 5, 12时, 相应团簇较稳定, 特别是Zr5B团簇的稳定性最高. 同时分析了ZrnB团簇的电子性质及磁性, 结果显示能隙随n值的增大出现奇偶振荡趋势, 特别是Zr12B团簇的能隙只有0.015 eV, 表明该团簇已具有金属性. 电荷转移随n值增大, 整体呈增大趋势, 除了二聚体ZrB, 电荷由B原子转移到Zr原子. 利用Mulliken布居分析得到二聚体ZrB(5.000 μB)和团簇Zr4B(3.000 μB)的磁矩较大, ZrnB团簇中总磁矩主要来自Zr原子的4d轨道.     

Binding energies of small lithium clusters (Li(n)) and hydrogenated lithium clusters (Li(n)H)

Large coupled cluster computations utilizing the Dunning weighted correlation-consistent polarized core-valence (cc-pwCVXZ) hierarchy of basis sets have been conducted, resulting in a panoply of internally consistent geometries and atomization energies for small Li(n) and Li(n)H (n=1-4) clusters. In contrast to previous ab initio results, we predict a monotonic increase in atomization energies per atom with increasing cluster size for lithium clusters, in accordance with the historical Knudsen-effusion measurements of Wu. For hydrogenated lithium clusters, our results support previous theoretical work concerning the relatively low atomization energy per atom for Li(2)H compared to LiH and Li(3)H. The CCSD(T)/cc-pwCVQZ atomization energies for LiH, Li(2)H, Li(3)H, and the most stable isomer of Li(4)H, including zero-point energy corrections, are 55.7, 79.6, 113.0, and 130.6 kcal/mol, respectively. The latter results are not consistent with the most recent experiments of Wu.     

Theoretical study of the geometries and dissociation energies of molecular water on neutral aluminum clusters Al(n) (n = 2-25)

Geometries and dissociation energies of water molecules on Al(n) (n = 2-25) clusters were investigated using density functional theory with all electron relativistic spin-polarized calculations under the generalized gradient approximation. An extensive structure search was performed to identify the low-energy conformations of Al(n)H(2)O complexes for each size. Optimal adsorption sites were assigned for low-energy isomers of the clusters. Size and site specific dependences were studied for the Al(n)H(2)O complexes in stabilities, geometries, adsorption energies, dissociation energies, Al-O bond lengths, and other characteristic quantities. The stabilities and geometries revealed that H atom in H(2)O is not inclined to bond with Al atoms. The most stable Al(n)H(2)O configurations for each size tend to correspond to the most stable bare Al(n) cluster except of Al(6) and Al(24) clusters. The HO bond lengths increase generally 0.01 ? with respect to the isolated H(2)O in all of the adsorption complexes. The dissociation energy of an isolated H(2)O into HO and H was 5.39 eV, which decreased about two-thirds to the energy range of 0.83-2.12 eV with the help of Al(n) clusters. In spite of the fluctuations, the dissociation energies of Al(n)H(2)O complexes rise with the size increasing as a whole. In addition, we also found that the bare Al(n) clusters with high vertical ionization potentials usually have high dissociation energies of H(2)O in the corresponding adsorption models. The energetically preferred spin-multiplicity of all the odd-n Al(n)H(2)O complexes is doublet, and it is singlet for all the even-n complexes with exception of Al(2)H(2)O which is triplet.     

The structural and electronic properties of Ag-adsorbed (SiO2)n (n=1-7) clusters

Equilibrium geometries, charge distributions, stabilities, and electronic properties of the Ag-adsorbed (SiO(2))(n) (n=1-7) clusters have been investigated using density functional theory with generalized gradient approximation for exchange-correlation functional. The results show that the Ag atom preferably binds to silicon atom with dangling bond in nearly a fixed direction, and the incoming Ag atoms tend to cluster on the existing Ag cluster leading to the formation of Ag islands. The adsorbed Ag atom only causes charge redistributions of the atoms near itself. The effect of the adsorbed Ag atom on the bonding natures and structural features of the silica clusters is minor, attributing to the tendency of stability order of Ag(SiO(2))(n) (n=1-7) clusters in consistent with silica clusters. In addition, the energy gaps between the highest occupied and lowest unoccupied molecular orbitals remarkably decrease compared with the pure (SiO(2))(n) (n=1-7) clusters, eventually approaching the near infrared radiation region. This suggests that these small clusters may be an alternative material which has a similar functionality in treating cancer to the large gold-coated silica nanoshells and the small Au(3)(SiO(2))(3) cluster.     

Geometries, stabilities, and electronic properties of small anion Mg-doped gold clusters: a density functional theory study

First-principle density functional theory is used for studying the anion gold clusters doped with magnesium atom. By performing geometry optimizations, the equilibrium geometries, relative stabilities, and electronic and magnetic properties of [Au(n)Mg]? (n = 1-8) clusters have been investigated systematically in comparison with pure gold clusters. The results show that doping with a single Mg atom dramatically affects the geometries of the ground-state Au(n+1)? clusters for n = 2-7. Here, the relative stabilities are investigated in terms of the calculated fragmentation energies, second-order difference of energies, and highest occupied?lowest unoccupied molecular orbital energy gaps, manifesting that the ground-state [Au(n)Mg]? and Au(n+1)? clusters with odd-number gold atoms have a higher relative stability. In particular, it should be noted that the [Au?Mg]? cluster has the most enhanced chemical stability. The natural population analysis reveals that the charges in [Au(n)Mg]? (n = 2-8) clusters transfer from the Mg atom to the Au frames. In addition, the total magnetic moments of [Au(n)Mg]? clusters exhibit an odd-even oscillation as a function of cluster size, and the magnetic effects mainly come from the Au atoms.