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THE JOURNAL OF CHEMICAL PHYSICS 122, 114310 2005

Geometric, electronic, and bonding properties of AuNM N = 1 7, M = Ni, Pd, Pt clusters


D. W. Yuan, Yang Wang, and Zhi Zenga
Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, Peoples Republic of China

Received 13 August 2004; accepted 4 January 2005; published online 18 March 2005 Employing rst-principles methods, based on density functional theory, we report the ground state geometric and electronic structures of gold clusters doped with platinum group atoms, AuNM N = 1 7, M = Ni, Pd, Pt. The stability and electronic properties of Ni-doped gold clusters are similar to that of pure gold clusters with an enhancement of bond strength. Due to the strong d-d or s-d interplay between impurities and gold atoms originating in the relativistic effects and unique properties of dopant delocalized s-electrons in Pd- and Pt-doped gold clusters, the dopant atoms markedly change the geometric and electronic properties of gold clusters, and stronger bond energies are found in Pt-doped clusters. The Mulliken populations analysis of impurities and detailed decompositions of bond energies as well as a variety of density of states of the most stable dopant gold clusters are given to understand the different effects of individual dopant atom on bonding and electronic properties of dopant gold clusters. From the electronic properties of dopant gold clusters, the different chemical reactivity toward O2, CO, or NO molecule is predicted in transition metal-doped gold clusters compared to pure gold clusters. 2005 American Institute of Physics. DOI: 10.1063/1.1862239
I. INTRODUCTION

A great number of investigations have been performed on heteroatomic or impurity-doped as well as homoatomic metal clusters,14 which indicate that the impurity atoms can strongly inuence geometric, electronic, and bonding properties of mixed clusters.3,5 So far, most theoretical and experimental studies about mixed metal clusters focus on alkali-metal and aluminum clusters to examine the jellium model and to clarify bonding characteristics between impurity atoms and host clusters. For example, the density functional calculations and mass spectra measurements on LinM M = Al, Be, Mg5,6 and NanM M = Li, Al, Mg, Ag, Au7 have conrmed that single-impurity alkali-metal clusters also conform to the jellium model and presented distinct electronic shell properties. The complicated electronic properties are found in pure aluminum clusters, and experimental and theoretical studies indicate that small aluminum clusters did not display magic numbers behavior.8 However, Gong and Kumar found some stable magic clusters with 40 valence electrons9 in impurity-doped icosahedral Al12X X = B, Al, Ga, C, Si, Ge, Ti, and As clusters; and recently, Li et al. primarily presented some all-metal aromatic molecules3 in M Al 4 M = Li, Na, or Cu clusters. Besides those mentioned above, there are many other studies which reported some particular geometric, electronic, and bonding properties in aluminum-based binary clusters compared with pure Al clusters.5,10 The noble-metal Cu, Ag, and Au clusters also show very pronounced electronic shell structures which have been
a

Author to whom correspondence should be addressed; Electronic mail: zzeng@theory.issp.ac.cn

found in alkali-metal clusters.1 Recently, gold clusters have been aroused considerable interests by chemists and physicists due to their unique physical and chemical properties, particularly, their catalytic activities in CO oxidation.11 In order to enhance the stability of gold clusters and improve their chemical activities, or examine the electronic shell structures in mixed gold clusters, many studies have been performed on impurity-doped or mixed gold clusters.1217 Bouwen et al.16 and Heinebrodt et al.17 investigated the bimetallic AunXm X = Cu, Al, Y, In, Cs clusters, and found the electronic shell effects. Koszinowski et al. found the reactions of bimetallic PtmAu+ n m + n cluster ions with O2 and CH4 exhibit the marked dependence on cluster composition, and their reactions toward O2 are consistently diminished as a function of gold content.12 Additionally, the impurity atom can modify and control the electronic structure of gold clusters, thus changing their chemical reactions for CO oxidation in Au3Sr cluster supported on a MgO100 surface.13 In the reported impurity-doped alkali-metal or Al clusters, the dopant delocalized or bonding electrons are just derived from s-, p-electrons of impurity atoms. However, recent experimental and theoretical investigations found that the delocalization of s- and d-electrons of transition metal TM atoms can considerably enhance the stability of Au or Si clusters doped with TM atoms.14,15,18 Neukermans et al. reported that the dopant-dependent number of delocalized electrons in gold clusters doped with open 3d-shell atoms are ascribed to the relative orbital sizes between 3d- and 4s-electrons and the energies required to promote an electron from the lled 4s2 shell to the 3d shell.15 At the same time, in icosahedral Au12M M = Mo, W clusters, the 18 electron rules were conrmed experimentally and theoretically due to
2005 American Institute of Physics

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the delocalization of s- and d-electrons of dopant atoms.14 Consequently, it is important to investigate TM-doped gold clusters, which can extend the cluster species and nd some novel gold-based cluster catalysts with higher stability and chemical reactivity. In this paper, using the rst-principles method based on density-functional theory, we systematically investigated the gold clusters doped with Pt-group atoms, AuNM N = 1 7, M = Ni, Pd, or Pt. Available studies1921 indicated that the Pd atom can be doped into Au clusters with the promotion of one electron from 4d to 5s orbitals. In the case of doping with nickel, Ni atom delivers just also one itinerant electron because of the small promotion energy from 3d84s2 to 3d94s1 with respect to other 3d transition elements.15 Only some small mixed gold clusters with Pt have been reported,22,23 and they exhibit fascinating chemical bonding and electronic properties due to the relativistic effects. Ni, Pd, and Pt atoms have the same number of valence electrons, but have evidently different ground electronic congurations and properties of excited states.2426 Therefore, these systems have a contribution in clarifying the inuence of the s-, d-electron of impurity atoms on geometric, electronic, and bonding properties of dopant gold clusters with respect to pure gold clusters.

FIG. 1. Binding energy per atom solid line and atomic dissociation energy dotted line for pure gold clusters. The 1D or 2D structures up to Au8 are presented.

III. RESULTS AND DISCUSSION

II. COMPUTATIONAL DETAILS

Our calculations were carried out using the Amsterdam density-functional ADF package27 with the local spin density approximation for exchange and correlation potential employing the Vosko-Wilk-Nusair GGA with PW91 Refs. 28 and 29 was employed for the density gradient correction to the exchange and correlation function. The triple-zeta basis set including two polarization functions based on Slatertype orbital30 was chosen. The 1s-4d orbitals for Au and Pt, 1s-3 p orbitals for Ni, and 1s-3d orbitals for Pd were kept frozen with the frozen core approximation. It was demonstrated that the relativistic effects are important for Au-type high Z system in dening geometric characteristics,31 therefore, the calculations were performed within the relativistic scheme with the zero-order regular approximation formalism without including the spin-orbit effects.32 Due to the open d-shell of dopant atoms, the convergence problems were met, particularly in Ni-doped clusters. So the electron smearing technique was employed with a fractional occupation number around Fermi level.33 In ADF code, the bond energies are calculated with respect to the spin restricted and symmetric atomic ground state. Then, to obtain the accurate ground state bond energies comparable to experimental value, we performed some calculations of atomic reference energies for Ni, Pd, Pt, and Au atoms following Ref. 34, and obtained the atomic correction terms for all bond energies. Geometric optimizations were based on a quasi-Newton approach, and the Hessian was updated in the process of optimization employing Broyten Fletcher Goldfarb Shanno BFGS method,35 until the convergence thresholds, i.e., 104 a.u. for the Cartesian gradient, and 105 a.u. for the energy were reached.

In order to discuss the effects of doped impurity atoms on gold clusters, we rst performed some calculations on pure gold clusters, AuN N = 2 8. The lowest energy structures are presented in Fig. 1. We did not nd threedimensional 3D ground state structures up to Au8, which is not in agreement with the results given by Ref. 36 but in line with that of Ref. 37. The 2D structure of Au8 is more stable with 0.41 eV than the bicapped octahedron structure. Furthermore, the 3D structure are more stable within nonrelativistic calculations. The planar ground state structures of gold clusters are ascribed to the hybridization between s- and d-electrons resulting from relativistic effects.31 The binding energies per atom are given in Fig. 1, which increase as the sizes of gold clusters. The atomic dissociation energies see Fig. 1 and second differences of energies of gold clusters see Fig. 7 exhibit pronounced even-odd alternations, which indicates that the clusters, with even valence electrons, keep higher stability compared with their vicinity clusters. Specically, Au6 is the most stable cluster among the considered gold clusters.
A. Structures and stability

Beginning with the available structures of dopant clusters and gold clusters, we obtained the lowest energy structures and some lower lying isomers of the AuNNi, AuNPd, and AuNPt, which are presented in Figs. 24, respectively. Except for Au2Ni and Au7Ni, all the lowest energy structures are very similar to each other for Ni-, Pd-, and Pt-doped clusters, but lower lying isomers have different structures. The detailed discussions for their structural characteristics are given as follows. The bond lengths of AuNi, AuPd, and AuPt dimers are 2.36, 2.50, and 2.47 respectively, which are less than that of Au2 dimer of 2.52 . The experimental value of the bond length of AuNi is 2.35 .38 For AuPd, the calculated values are 2.51 and 2.56 ,20,21 while for AuPt they are 2.60 .23 The bond energies are 2.51, 1.88, and 2.55 eV for AuNi, AuPd, and AuPt, respectively, compared with 2.36 eV for

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Properties of AuNM

J. Chem. Phys. 122, 114310 2005

FIG. 2. The optimized structures for Ni-doping gold clusters AuNNi N = 2 7. The former brackets refer to relative energy of lower lying energy structure with respect to corresponding ground state structure and the latter is the spin state of cluster. The data in square parenthesis refers to the magnetic moment in B and Mulliken charge in e of the Ni atom orderly.

FIG. 3. The optimized structures for Pd-doping gold clusters, AuNPd N = 2 7. The former brackets refer to relative energy of lower lying energy structure with respect to corresponding ground state structure and the latter is the spin state of cluster. The data in square parenthesis refer to the magnetic moment in B and Mulliken charge in e of Pd atom orderly.

Au2. The smallest bond length for AuNi should originate from the smallest atomic radius, however, the strongest bonding of AuPt dimer results from the d-electron contributions.22 The optimized ground state structure of Au2Ni, 2a-Ni presented in Fig. 2, has Cs symmetry with an apex angle of 142.8, and the linear structure with central Ni atom is almost degenerate with the energy difference of 0.07 eV. While the triangle structure with an apex angle of 76.5 is less stable with 0.29 eV in energy higher than the Cs geometry of 2a-Ni presented in Fig. 2. In the cases of Au2Pd and Au2Pt, both the lowest energy conformers 2a-Pd and 2aPt have C2v symmetric triangle structures with apex angles of 61.7 and 66.2, respectively. This structure has been found in Ref. 21 for Au2Pd cluster but different lower lying energy isomers are found in Figs. 3 and 4. Au3 keeps a linear ground state structure in our present calculations. Interestingly, the Pd or Pt dramatically changes the ground state structures of dopant gold clusters containing three atoms, which results from the bonding interaction between the d-electron of impurity atoms and the 5d-electron of Au due

to their open d orbitals and relativistic effects. While with very minor contributions of d orbital to bonding in Au2Ni, which has been found in AuNi dimer,39 its lowest energy structure retains a linear state. To understand these discrepancies further, we examine their highest occupied molecular orbitals HOMOs further. In 2a-Pd and 2a-Pt, their HOMOs mainly consist of d orbitals dx2y2 , dz2 of impurity atoms with minor contributions of Au5d. Because the nodal planes of Pd or Pt d orbitals are located at the cluster planes, the weak interaction between Au and Pd Pt exists. However, the triangle structures can increase the AuAu bond interaction so as to obtain the lowest energy structures. In 2a-Ni, though its HOMO of spin at 5.96 eV energy level is also contributed by Ni3d and Au5d, the HOMO of spin at 6.04 eV energy level is mainly composed of 81.4% of Au6s and 10.3% of Ni4 p. The linear structure with Ni located at center site can maximize the bonding interaction of Ni4 p and Au6s, and the bonding interaction forms in the HOMO, just as the bonding interaction between Zn4 p and Au6s in Au2Zn cluster.40 For 2b-Ni, both HOMOs in spin and spin are contributed from Au6s 80.5% for spin , 82.0% for spin and Ni4 p 11.1% for spin , 10.2% for

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FIG. 4. The optimized structures for Pt-doping gold clusters, AuNPt N = 2 7. The former brackets refer to the relative energy of lower lying energy structures with respect to corresponding ground state structure and the latter is the spin state of cluster. The data in square parenthesis refer to the magnetic moment in B and Mulliken charge in e of Pt atom orderly.

spin . The character of HOMO and the lowest unoccupied molecular orbital LUMO of Au2M M = Ni, Pd, and Pt can intuitively be shown by their isosurface plots, which are presented in Fig. 5. In the HOMO and LUMO of spin of Au2Ni, the considerable s, p contributions are found. While HOMO and LUMO of spin are composed of d orbitals of Ni and Au. In the HOMOs of Au2Pd and Au2Pt, the d d

interaction between Au and Pd or Pt is very week, and the triangle structure can enhance the bonding of Au atoms. At the same time, the s, d contributions are found in LUMOs of Au2Pd and Au2Pt clusters. Then the different bonding properties between impurities and gold atoms determine their ground state structural characteristics. For N = 3, the gold clusters doped with Ni, Pd, and Pt all have C2v rhombus ground state structures. Some Y-shaped lower lying structures are obtained with the impurity atoms occupying center or apex positions. Above their lowest energy structures, we found three Cs rhombus structures 3dNi, 3c-Pd, and 3c-Pt at 0.58, 0.48, and 0.28 eV, respectively, for Au2Ni, Au2Pd, and Au2Pt. Moreover, we obtain an isomer 3d-Pd with tetrahedron structure for Au3Pd, which is less stable than 4a-Pd by 0.51 eV. In Ref. 21, the rhombus ground state structures with three isomers, which are planar or linear structures, are presented, while in Ref. 20 the kiteshaped conformer is the lowest energy structure. To explain the geometric characteristics onwards, we likewise examine the compositions of their HOMOs. The HOMOs consist of 72.7% of Ni3d dz2, 65.0%; dx2y2, 7.7% and 13.1% of Au6d dxy, 7.9%; dz2, 5.2%; 83.5% of Pd4d dz2, 8.3%; dx2y2, 75.3% and 9.5% of Au6d dyz, 7.4%; dx2y2, 2.1%; and 83.1% of Pt6d dz2, 9.9%; dx2y2, 73.2% and 7.0% of Au6d dyz, 4.0%; dx2y2, 3.1% for 3a-Ni, 3a-Pd, and 3a-Pt, respectively. The signicant d orbital character of impurity atoms in the frontier orbitals is found. It is the same case in the following Pt-group-doped gold clusters. The unique d d interaction between impurities and gold atoms would impact the geometrical structures and stability of Pt-group-doped gold clusters. In the case of Au4M M = Ni, Pd, and Pt, their most stable structures are planar trapezoidal shaped with impurities centered in the middle of bottom lateral. The isomers 4b-Ni, 4b-Pd, and 4b-Pt, of which the impurity atoms occupy apex positions, are found at the energies of 0.24, 0.24, and 0.47 eV, respectively, above their corresponding ground state structures. Two 3D isomers 4c-Ni, 4c-Pd are presented for Ni- and Pd-doped gold clusters. While the isomer of Au4Pt keeps 2D structure up to the relative energy of 0.57 eV see 4d-Pt in Fig. 4. Evidently, the impurity atoms tend to bond with gold atoms as much as possible in their most stable 2D structures. Lately, Neukermans et al.15 found some very stable clusters for Au5X+ X = V, Cr, Mn, Fe, and Co experimentally,

FIG. 5. The highest occupied molecular orbital HOMO and lowest unoccupied molecular orbital LUMO isosurfaces of Au2M Ni, Pd, and Pt clusters. HOMO-a and HOMO-b represent the HOMO in and spin, respectively. The same to LUMO-a and LUMO-b.

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and they suggested that these systems should contain six free electrons corresponding to an oblate shell closure in the ClemengerNilsson model.41 At the same time, theoretical calculations indicated that the enhanced stability of Au5Zn+ can be regarded as a aromatic bimetallic cluster with six delocalized s-electrons.42,43 The bonding interactions of Zn4 p and Au6s enhance the stability of planar structure for Au5Zn+, and its ground state conformer has a triangular structure with the impurity atom located on a side of the triangle. Here we found similar lowest energy structures for Au5M clusters. Though Pd or Pt atoms can donate their individual one s valence electron into the delocalized electrons of clusters, 5a-Pd and 5a-Pt do not retain more stability than their other involved dopant clusters, while Au5Ni is the most stable structure, which will be discussed in the followings. Three lower lying energy isomers are given, which have similar geometric structures with different energy orderings for the three types of dopant gold clusters. Interestingly, the 3D structures, 5b-Ni, 5b-Pd, and 5d-Pt, can be obtained by removing the central impurity atoms of their distortion pentagonal structures 5c-Ni, 5c-Pd, 5b-Pt to top sites from the planes approximately formed by gold atoms. In the cases of Ni- and Pd-doped clusters, the 3D structures are more stable with 0.08 and 0.01 eV than their corresponding distortion pentagonal structures, but the case reverses in Pt-doped clusters, and 5d-Pt has the highest relative energy of 0.49 eV. We found three high symmetric lowest energy structures, planar hexagon with the impurity atoms located at the center sites in our calculations for Au6M clusters, which can be derived from the distorted pentagonal isomers of Au5M . We consider that the high symmetric structures are determined by the d d bonding interaction between Pt-group and gold atoms. The other planar isomers can be obtained by adding an atom to triangle structures, 5a- M M = Ni, Pd, Pt and 5c-Pt. The 3D lower lying energy isomers of the pentagonal bipyramid with the impurity atoms occupying one apex, 6c-Ni and 6b-Pt are less stable with 0.25 and 0.42 eV, respectively, but with 0.98 eV for 6d-Pt which is almost degenerate with the planar structure 6c-Pt. Two square pyramid structures capped by two gold atoms on two conjoint faces are less stable with the relative energies of 0.49 or 0.48 eV for Ni and Pd doping, respectively. From these discussions, we see that Pt-doped Au clusters retain the planar structures with higher stability than the two other cases. In the case of Au7M , we obtained the most stable conformers with two lower lying isomers. A 3D structure obtained by adding one Au atom on top of Ni site in 6d-Ni structure, is the lowest energy structure for Au7Ni, which is only 0.08 eV lower than the planar structure derived from 6a-Ni by adding a gold atom to one side. However, the cases are reversed in Au7Pd and Au7Pt, and the planar structures, 7a-Pd, 7a-Pt, are more stable with the energies of 0.12 and 0.36 eV than 3D structures, respectively. Three similar planar isomers, 7c-Ni, 7c-Pd, and 7c-Pt, are given by replacing one Au atom in pure Au8 cluster, and are found lying 0.14, 0.44, and 0.53 eV above their lowest energy structures. From the ground state structures and their isomers of Pt-groupdoped gold clusters, we see Ni atom induces a structure transferring from 2D to 3D more easily.

The most stable planar structures are found in AuNM N = 3 7, M = Ni, Pd, and Pt apart from Au7Ni. Some structures can be obtained by replacing one Au atom of corresponding pure gold clusters with impurity atoms, such as 4a- M , 5a- M , and 6a- M M = Ni, Pd, and Pt. The coordination number of impurity atoms increases with the size of cluster. The unique bonding interactions between Pt-group metals and gold atoms result in the lowest energy structures with high symmetry, namely, 6a- M M = Ni, Pd, and Pt, which differs from Zn-doped cases.40 The same lowest energy structures are presented in Pd- and Pt-doped gold clusters. Only one 3D lowest energy structure is found in 7aNi which is almost degenerate with the planar isomer, 7bNi. The minor differences between Ni-doped and Pd- or Ptdoped clusters conrm the important role of relativistic effects in determining the planar stable structures of gold clusters.31 In order to discuss the stability of the AuNM M = Ni, Pd, and Pt clusters, we calculated the relative bond energies with respect to their corresponding pure gold clusters, atomic dissociation energies, and the second differences of energy for the most stable dopant gold clusters see Figs. 6 and 7. The bond energies are obtained with the consideration to the atomic reference energies corrections, which have been dened by the fragment approach.47 The atomic dissociation energy is given by EDAuNM = EBAuN EBAuNM for impurity atoms and EDAuNM = EBAuN1M EBAuNM for gold atoms; and the second difference of energy by 2EAuNM = EBAuN+1M + EBAuN1M 2EBAuNM , where M refers to Ni, Pd, or Pt atom, and EB is the bond energy of clusters considering atomic correction energy. The relative bond energies alter with odd-even oscillations as a function of the number of gold atoms, in particular, for Pt-doped gold clusters. Moreover, the order of bonding strength of their corresponding dopant clusters is Pt Ni Pd. The bonding properties of Pt-group doped gold clusters should be attributed to the different bonding interactions between impurity elements and gold atoms originated by the different atomic ground states and relativistic effects of impurity atoms. The atomic dissociation energies of Ni, Pd, and Pt are presented in Fig. 6 for the most stable clusters. An odd-even alteration is also found, in particular, for Ni-doped clusters. Compared to the available atomic dissociation energies presented in Fig. 6 of the corresponding pure Pt-group clusters, the larger bond energy of Ni atom is obtained, in particular, for smaller clusters; and the case is reversed for Pt atom; while the case is more complicated for Pd atom. Moreover, Pt atom has the largest atomic dissociation energy due to the strongest d d interaction between Au and Pt atoms. The atomic dissociation energies of Au present different variation tendencies as a function of the size of dopant clusters in Ni-, Pd-, and Pt-doped gold clusters. An odd-even alteration for gold atomic dissociation energies is found in Ni-doped gold clusters as pure gold clusters, while it is not for Pd- and Pt-doped gold clusters. Moreover, the atomic bond energies of gold make the increasing in dopant gold clusters containing even-number gold atoms compared with the same size

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J. Chem. Phys. 122, 114310 2005

FIG. 7. The second difference of energy of AuN solid line, AuNNi dotted line, AuNPd dashed line, and AuNPt long dashed line

strong s d and d d interaction due to the different atomic congurations and relativistic effects of impurity atoms. The different bonding properties subjected to the different properties of s- and d-electron of impurity atoms will be discussed in the following section.
B. Electronic structures and bonding properties

FIG. 6. The relative bond energies of dopant gold clusters with respect to their corresponding pure gold clusters dashed line and the dissociation energies per atom: Au atom solid line, impurity atom dotted line. The experimental and theoretical data of atomic dissociation energies in Pt-group clusters long dashed line with hollow square are obtained from Refs. 4446. a, b, and c correspond to AuNNi, AuNPd, and AuNPt, respectively.

gold clusters. Therefore, it shows that the Pt-group atoms can enhance the stability of dopant gold clusters with respect to pure gold clusters. The second difference of energy, shown in Fig. 7, manifests that the Ni-doped clusters keep the same pattern of stability with pure gold clusters, and Au5Ni is the most stable cluster in the Ni-doped clusters. While no odd-even oscillations are observed in AuNPd and AuNPt, moreover, Au6M M = Pd and Pt appears to be more stable due to their high symmetry geometric structures. The inuence of impurity atoms on the bonding strength and stability of Pt-group-doped gold clusters depends on the number of gold atoms and atomic ground state congurations of impurity atoms. A stronger bonding interaction is found in dopant gold clusters containing even-numbered gold atoms. In Ni-doped clusters containing even-numbered gold atoms, the two s electrons are donated from Ni; but just only one for the clusters of odd-number gold atoms. While, for Pd- and Pt-doped clusters contained even-number gold atoms, the stronger bonding interaction results from the

In order to analyze the bonding interaction between impurity metal and gold atoms, we examine the Mulliken atomic charges and magnetic moments of Ni, Pd, and Pt atoms in the most stable dopant clusters see Figs. 24 respectively. The negligible net charges are found on Ni and Pt atoms, but a few atomic charges are existed in Pd-doped gold clusters. The charge transfer does mainly come out of the differences in electronegativity EN. However, the small differences of EN between impurities and gold atoms cannot result in evident charge transfer. The charge transfer in Pddoped clusters may be related with the interaction between 6s of Au and 4d of Pd. The spin state total magnetic moment of cluster will have inuence on its reactivity towards gas molecules, particularly the spin triplet O2 molecule.48 We found that Ni atoms have the moment ca. 1.00B in the Ni-doping gold clusters containing odd-numbers of gold atoms, while for Au2Ni and Au4Ni, 1.45B and 1.35B are presented, respectively. In Au6Ni, Ni has not net magnetic moment. The spin conguration of Au6Ni is ascribed to the high symmetric geometric structure. In AuNPd and AuNPt clusters, Pd and Pt have similar magnetic properties see Figs. 3 and 4, respectively. The values of moments of Pd and Pt atoms are 0.81B and 0.95B in AuPd and AuPt dimers. All Pd- and Pt-doped gold clusters containing evennumbers of gold atoms are shown to be spin singlet, which results in zero net spin for Pd and Pt atoms. Moreover, the net magnetic moments of Pd and Pt atoms signicantly decrease with the increasing of the cluster size in odd-number gold clusters doped with Pd or Pt. In AuNNi, the total magnetic moments are mainly contributed from Ni atoms, while the spin moments tend to spread over the whole of the clusters in AuNPd and AuNPt clusters. The different magnetic properties in Pt-group-doped gold clusters are related to different atomic properties of impurity atoms in ground state and lower lying excited states.

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J. Chem. Phys. 122, 114310 2005

FIG. 9. The GPDOS of the s orbitals of impurity atoms in a Au5M and b Au6M . FIG. 8. The bond energies of AuNNi solid line, AuNPd dotted line, or AuNPt dashed line are decomposed into relative orbital interaction Eoi a and relative steric interaction E0 b with respect to AuN.

As mentioned above, 3d84s2 state is almost degenerate with that of 3d94s1 in the Ni atom. Therefore, one or two electrons can be contributed into Ni-doped Au clusters according to the amount of gold atoms. The spin doublet and triplet states are found in Ni-doped gold clusters. Though the promotion energy from 4d105s0 to 4d95s1 is 0.95 eV for the Pd atom, the bond of AuPd could be formed through orbital between 6s of Au and 5s of Pd with one electron promoted from 4d to 5s of Pd.19 For Pt-doped clusters, 5d96s1 is more stable than 5d106s0 with 0.48 eV, so the spin doublet state is found in AuNPd and AuNPt by odd-N with a few magnetic moments on Pd and Pt atoms. The decreasing of the magnetic moments of Pd and Pt atoms is reasoned by the d d and s d interaction originated from relativistic effects. Because of the high promotion energy, two-electron donation is energetically unfavorable in even-N Pd- and Ptdoped gold clusters. Then the spin singlet state is shown in Pd- and Pt-doped gold cluster containing even-number gold atoms. Meanwhile, we expect that the local magnetic moment of dopant gold clusters with single magnetic atom would decrease with the increasing of the size of the clusters. The different atomic status and electronic properties of doped atoms give rise to different bonding strength and characteristics in dopant gold clusters, as mentioned above. Here, we further discuss their bonding properties by bond energy analysis in detail. In ADF code, using the Mokokuma-type energy decomposition method,49 the overall bond energy EB

is divided into two major components as EB = E prep + Eint, where E prep corresponds to the amount of energy required to deform the separated fragments from their equilibrium structure to the geometry they acquired in the overall molecule and to excite them to their valence electronic conguration. Eint can be further decomposed into E0 and Eoi, where E0 termed steric interaction includes the term electrostatic interaction and the other Pauli or steric repulsion; while Eoi originates from relaxation of the wave function corresponding to its fragments, which is named orbital interaction. Figure 8 gives the relative orbital interaction Eoi Fig. 8a and steric interaction E0 Fig. 8b for the lowest energy structures. Evidently, Pd-doped gold clusters present the weakest orbital interaction and steric interaction compared with Ni-, Pt-doped gold clusters, as well as pure gold clusters. The strongest steric repulsion of Pt-doped gold clusters can be attributed to the large kinetic repulsion of valence electrons of Pt due to the overlap of valence and deep core orbitals. The large promotion energy of electrons for Pd atom results in different properties of valence electrons in Pddoped gold clusters, which reduces the steric repulsion interaction. Ni-doped gold clusters present a similar steric interaction to pure gold clusters with exception of 6a-Ni and 7a-Ni. The strongest orbital interaction for Pt-doped gold clusters is also related to the strong d d and s d interactions due to the relativistic effects. For Ni-doped gold clusters, although dopant Ni atom reduces the relativistic effects comparing with Au atom, the strong 4sNi 3dNi and 4sNi 6sAu interaction can enhance their orbital interactions. However, the weakest orbital interaction in Pd-doped

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Yuan, Wang, and Zeng

J. Chem. Phys. 122, 114310 2005

FIG. 10. The PDOS of a Au5Ni, b Au5Pd, and c Au5Pt. The vertical dotted line refers to Fermi level.

FIG. 11. The PDOS of a Au6Ni, b Au6Pd, and c Au6Pt. The vertical dotted line refers to Fermi level.

clusters should be determined by the properties of 5s of Pd atom. Then, the strength of steric interaction and orbital interaction are determined by the properties of delocalized and core orbital electrons cooperatively. The stronger bond interaction is predicted in TM-doped gold cluster than the corresponding pure gold clusters. A variety of density of states DOS for 5a- M and 6aM M = Ni, Pd, and Pt are given in Figs. 913, which show the atomic properties of impurities and bonding interactions intuitively. The gross population density of states GPDOS present the weight factor of a basis function in the molecular orbitals determined by means of a Mulliken population analysis. From GPDOS of s orbitals of impurities, we found that all of them have made a large contribution to the states below the Fermi levels, which indicates that one of the 4d-electrons can be promoted to 5s orbitals in Pd atoms resulting in stable bonding interaction between Pd and the host section in Pd-doped gold clusters. However, the order of magnitude of GPDOS of Pd5s is evidently lower than that of the others around the energy of 10 eV. The GPDOS of Pt6s shifts to lower energy compared with that of Ni4s and Pd5s, which can give rise to a strong interaction with 5d electron of Pt or Au atoms. In Figs. 10 and 11, we present the projected density of states PDOS for 5a- M and 6a- M M

= Ni, Pd, and Pt. The PDOS of a basis function provides similar information to GPDOS, but the weight factor is determined by the projection of the function onto the molecular orbitals. In all cases, the PDOS of dopant d electrons are located around Fermi levels and higher than corresponding PDOS of Au d electrons with a little crossing and overlap. The increasing of electronic states around the Fermi level of dopant gold clusters contributed by impurity atoms enhances the reactivity toward O2, NO, and CO, etc.13 Thus, the TMimpurities will optimize the catalytic properties of Au clusters. In 5a- M , the s electrons of gold or dopant atoms spread over the d band, but in 6a- M , the PDOS of dopant s-electron shows a peak below the d band of gold, which is also seen from the GPDOS in Fig. 9. The dopant s-electron characters are related to the different interactions between the dopant s and s-electron contributed by gold atoms. The contribution to the overlap between the d band of gold and dopant d electron increases from Ni-doped to Pt-doped clusters, which results in different d d interaction between dopant and host gold atoms. We examine their bonding properties of 5a- M and 6a- M from the overlap population density of states OPDOS further see Figs. 12 and 13. First of all, we see that the bonding strength of d d between dopant and gold atoms increases from Ni to Pt. The interactions between d electron of gold atoms and delocalized s electron have no

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114310-9

Properties of AuNM

J. Chem. Phys. 122, 114310 2005

FIG. 12. The OPDOS of a Au5Ni, b Au5Pd, and c Au5Pt. The vertical dotted line refers to Fermi level.

FIG. 13. The OPDOS of a Au6Ni, b Au6Pd, and c Au6Pt. The vertical dotted line refers to Fermi level.

evident differences in 5a- M and 6a- M . However, the interactions between the dopant s and host s-electron present signicant differences, and it is found to be the weakest interaction in 5a-Pd and 6a-Pd compared with the other dopant gold clusters. Again, from the OPDOS plots the negligible overlap between d electron of Ni and delocalized s electron is found in Ni-doped clusters with respect to that of Pd- and Pt-doped gold clusters. From the above discussion, we have reached our conclusions. First, the special d-electron properties present the strong steric interaction and orbital interaction in Pt-doped clusters, and the s-electron properties of dopant atoms signicantly affect their bonding strength. Second, the strong d d and s d interactions determine the geometric and bonding properties in 4dPd and 5dPt TM-doped gold clusters. Finally, the properties of dopant valence electrons are changed with the number of gold atoms. Figure 14 gives the vertical detachment energies vDEs for the most stable pure and dopant gold clusters, which are dened by the energy differences between anion clusters adding one electron and neutral clusters keeping the same geometric structures. The odd-even alterations are shown markedly in pure and Ni-doped gold clusters. While in AuNPd and AuNPt no even-odd behavior is found as their stability. The existed theoretical and experimental investigations reported odd-even alterations of electron afnities in

AuNPdN = 1 4 clusters. Here the obtained vDEs are in agreement with the available data with exception of the value of Au2Pd.1921 This discrepancy may be resulted from the different ground state structures of Au2Pd between the different calculation methods.20 Therefore we expect that the vDEs of Pd- and Pt-doped gold clusters would not keep evident odd-even alterations, because of the interplay of s- and d-electron of dopant atoms. The changes of electronic properties of dopant gold clusters will change their chemical reactivity towards the gas molecules, such as O2, NO, CO.

FIG. 14. The vertical detachment energy vDE of AuN solid line, AuNNi dotted line, AuNPd dashed line, and AuNPt long dashed line.

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114310-10

Yuan, Wang, and Zeng

J. Chem. Phys. 122, 114310 2005 Science 291, 859 2001. E. Janssens, S. Neukermans, and P. Lievens, Curr. Opin. Solid State Mater. Sci. in press. 5 S. Shetty, S. Pal, and D. G. Kanhere, J. Chem. Phys. 118, 7288 2003. 6 H. Cheng, R. N. Barnett, and U. Landman, Phys. Rev. B 48, 1820 1993; M. Deschpande, A. Dhavale, R. R. Zope, C. Chacko, and D. G. Kanhere, Phys. Rev. A 62, 063202 2000; T. Baruah, D. G. Kanhere, and R. R. Zope, ibid. 63, 063202 2001. 7 P. Fantucci, V. Bonai-Kouteck, W. Pewestort, and J. Kouteck, J. Chem. Phys. 91, 4229 1989; U. Rothlisberger and W. Andreoni, Int. J. Mod. Phys. B 6, 3675 1992; Chem. Phys. Lett. 198, 478 1992; A. Dhavale, D. G. Kanhere, C. Majumder, and G. P. Das, Eur. Phys. J. D 6, 495 1999; R. Antonie, D. Rayane, A. R. Allouche, M. Aubert-Frcon, E. Benichou, F. W. Dalby, Ph. Dugourd, M. Broyer, and C. Guet, J. Chem. Phys. 110, 5568 1999; A. Dhavale, V. Shah, and D. G. Kanhere, Phys. Rev. A 57, 4522 1998; R. R. Zope, S. A. Blundel, C. Guet, T. Baruah, and D. G. Kanhere, ibid. 63, 043202 2001; T. Baruah, S. A. Blundell, and R. R. Zope, ibid. 64, 043202 2001. 8 X. Li, H. B. Wu, X. B. Wang, and L. S. Wang, Phys. Rev. Lett. 81, 1909 1998; M. D. Deshpande, D. G. Kanhere, I. Vasiliev, and R. M. Martin, Phys. Rev. B 68, 035428 2003. 9 X. G. Gong and V. Kumar, Phys. Rev. Lett. 70, 2078 1993. 10 A. Dhavale, D. G. Kanhere, S. A. Blundell, and R. R. Zope, Phys. Rev. B 65, 085402 2002; S. N. Khanna, B. K. Rao, and P. Jena, ibid. 65, 125105 2002. 11 M. Valden, X. Lai, and D. W. Goodman, Science 281, 1647 1998; H.-G. Boyen et al., ibid. 297, 1533 2002; J. Li, X. Li, H. J. Zhai, and L. S. Wang, ibid. 299, 864 2003. 12 K. Koszinowski, D. Schrder, and H. Schwarz, ChemPhysChem 4, 1233 2003. 13 H. Hkkinen, S. Abbet, A. Sanchez, U. Heiz, and U. Landman, Angew. Chem., Int. Ed. 42, 1297 2003. 14 P. Pyykk and N. Runeberg, Angew. Chem., Int. Ed. 41, 2174 2002; X. Li, B. Kiran, J. Li, H. J. Zhai, and L. S. Wang, ibid. 41, 4786 2002. 15 S. Neukermans, E. Janssens, H. Tanaka, R. E. Silverans, and P. Lievens, Phys. Rev. Lett. 90, 033401 2003. 16 W. Bouwen, F. Vanhoutte, F. Despa, S. Bouckaert, S. Neukermans, L. T. Kuhn, H. Weidele, P. Lievens, and R. E. Silverans, Chem. Phys. Lett. 314, 227 1999;. 17 M. Heinebrodt, N. Malinowski, F. Tast, W. Branz, I. M. L. Billas, and T. P. Martin, J. Chem. Phys. 110, 9915 1999. 18 H. Hiura, T. Miyazaki, and T. Kanayama, Phys. Rev. Lett. 86, 1733 2001; S. N. Khanna, B. K. Rao, and P. Jena, ibid. 89, 016803 2002; S. N. Khanna, B. K. Rao, P. Jena, and S. K. Nayak, Chem. Phys. Lett. 373, 433 2003; P. Sen and L. Mitas, Phys. Rev. B 68, 155404 2003; G. Mpourmpakis, G. Froudakis, A. N. Andriotis, and M. Menon, ibid. 68, 125407 2003. 19 K. Koyasu, M. Mitsui, A. Nakajima, and K. Kaya, Chem. Phys. Lett. 358, 224 2002. 20 Z. J. Wu, S. H. Zhou, J. S. Shi, and S. Y. Zhang, Chem. Phys. Lett. 368, 153 2003. 21 B. R. Sahu, G. Maofa, and L. Kleinman, Phys. Rev. B 67, 115420 2003. 22 R. Ramachandran, N. C. Payne, and R. J. Puddephatt, J. Chem. Soc., Chem. Commun. 1989, 128; N. C. Payne, R. Ramachandran, G. Schoettel, J. Vittal, and R. J. Puddephatt, Inorg. Chem. 30, 4048 1991. 23 Dingguo Dai and K. Balasubramanian, J. Chem. Phys. 100, 4401 1994. 24 S. P. Walch and C. W. J. Bauschlicher, in Comparison of Ab Initio Quantum Chemistry with Experiment, edited by R. J. Bartlett D. Reidel, Dordrecht, 1985, p. 17. 25 C. E. Moore, Natl. Bur. Stand. Circ. U. S. 1, 467 1949. 26 C. F. Fischer, The Hartree-Fock Method for Atoms Wiley, New York, 1977, pp. 2888. 27 ADF 2003, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, Netherlands www.scm.com. 28 S. H. Vosko, L. Wilk, and M. Nusair, Can. J. Phys. 58, 1200 1980; S. H. Vosko and L. Wilk, J. Phys. C 15, 2139 1982. 29 J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 1992. 30 E. V. Lenthe and E. J. Baerends, J. Comput. Chem. 24, 1142 2003. 31 H. Hkkinen, M. Moseler, and U. Landman, Phys. Rev. Lett. 89, 033401 2002. 32 E. V. Lenthe, E. J. Baerends, and J. G. Snijders, J. Chem. Phys. 99, 4597 1993; 101, 9783 1994; E. V. Lenthe, J. G. Snijders, and E. J. Baerends, ibid. 105, 6505 1996; E. V. Lenthe, A. E. Ehlers, and E. J. Baerends,
4

From our results, we predict that the odd-even alteration of the reactivity of O2 can be found on Ni-doped gold clusters, but does not occur on Pd- and Pt-doped gold clusters.
IV. SUMMARY

The geometric, electronic, and bonding properties of Ptgroup doped gold clusters have been investigated using rstprinciples methods. The planar structures are energetically favorable in AuNPd and AuNPt N = 2 7. While Ni can accelerate the conversion of 2D to 3D structures of Ni-doped clusters with respect to corresponding AuN clusters, and we found the most stable 3D structure in Au7Ni cluster, which is almost degenerate with its corresponding planar structure. The relative stable planar structures of Pt-doped gold clusters can be attributed to the strong relativistic effects of Au and Pt. The stability and bonding strength depend on the atomic ground properties of Pt-group metals. The magic cluster is also found in Ni-doped gold clusters similar to the pure gold clusters. While the stability of Pd- and Pt-doped gold clusters is evidently changed due to the relative strong bonding interaction contributed by d electrons. The inuence of impurity atoms on bond energies of dopant gold clusters is altered with odd-even oscillations as the number of gold atoms. Furthermore, Ni and Pt atoms can enhance the bonding strength distinctly compared with some minor changes in Pd-doped clusters. The different atomic ground state properties of Pt-group metals determine the bonding and electronic properties of dopant gold clusters. Ni can donate one or two electrons into gold clusters, while Pd and Pt only contribute one electron with the promotion of one electron from 4d to 5s in AuNPd. In Pd-doped gold clusters, a few charge transfers have been found due to the interaction between Au6s and Pd5d. The lesser contribution of 5s of Pd into delocalization electrons of dopant clusters results in weaker bonding strength than that of Ni- and Pt-doped clusters. The d d and s d interaction between impurities and gold atoms can modify the electronic properties of dopant gold clusters markedly, in particular for Pd and Pt, which will change the chemical reactivity between gold clusters and gas molecules, such as O2, NO, and CO, so that the catalytic properties are hoped to be improved with the transition metal doped gold clusters.
ACKNOWLEDGMENTS

This work was supported by the National Science Foundation of China under Grant Nos. 10374091 and 90103038, the Special Funds for Major State Basic Research Project of Fhina under Grant No. G1999064509, and Knowledge Innovation Program of Chinese Academy of Sciences Grant No. KJCX2-SW-W11. Part of the calculations were performed in Center for Computational Science, Hefei Institutes of Physical Sciences.
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1 2

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