CO chemisorption on the surfaces of the golden cages

Huang, Wei; Bulusu, Satya S.; Pal, Ranjan; Zeng, Xiao Cheng; Wang, Lai-Sheng

doi:10.1063/1.3273326

Cited by 32 publications

(38 citation statements)

References 64 publications

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“…Since simulated PES spectra with the inclusion of SO effects have not been reported for gold clusters in the size range of Au 9 − -Au 12 − , they are presented here as references. We have found that the inclusion of SO effects can yield simulated PES spectra in much better agreement with the experimental PES data, 42,57 making it possible to identify structures with much higher confidence on the basis of the simulated PES spectra. This is important because of the limited accuracy in the DFT-based energetic information among closely lying structural isomers.…”

Section: Theoretical Results and Discussionmentioning

confidence: 64%

“…We recently found that the inclusion of spin-orbit ͑SO͒ effects 56 is essential to achieve quantitative agreement between simulated and measured photoelectron spectra for Au clusters. 42,57 In the current work, we used the PBE0 hybrid functional and CRENBL basis set ͑i.e. the large effectivecore-potential orbital basis for use with the small core poten-tials͒ including SO effects, as implemented in NWCHEM 5.1.1, 58,59 to calculate the photoelectron spectra of the lowlying isomers.…”

Section: Theoretical Methodsmentioning

confidence: 99%

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Observation of earlier two-to-three dimensional structural transition in gold cluster anions by isoelectronic substitution: MAun− (n=8–11; M=Ag,Cu)

Wang

Pal

Huang

et al. 2010

The Journal of Chemical Physics

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The effects of isoelectronic substitution on the electronic and structural properties of gold clusters are investigated in the critical size range of the two-dimensional (2D)-three-dimensional (3D) structural transition (MAu(n)(-), n=8-11; M=Ag,Cu) using photoelectron spectroscopy and density functional calculations. Photoelectron spectra of MAu(n)(-) are found to be similar to those of the bare gold clusters Au(n+1)(-), indicating that substitution of a Au atom by a Ag or Cu atom does not significantly alter the geometric and electronic structures of the clusters. The only exception occurs at n=10, where very different spectra are observed for MAu(10)(-) from Au(11)(-), suggesting a major structural change in the doped clusters. Our calculations confirm that MAu(8)(-) possesses the same structure as Au(9)(-) with Ag or Cu simply replacing one Au atom in its C(2v) planar global minimum structure. Two close-lying substitution isomers are observed, one involves the replacement of a center Au atom and another one involves an edge site. For Au(10)(-) we identify three coexisting low-lying planar isomers along with the D(3h) global minimum. The coexistence of so many low-lying isomers for the small-sized gold cluster Au(10)(-) is quite unprecedented. Similar planar structures and isomeric forms are observed for the doped MAu(9)(-) clusters. Although the global minimum of Au(11)(-) is planar, our calculations suggest that only simulated spectra of 3D structures agree with the observed spectra for MAu(10)(-). For MAu(11)(-), only a 3D isomer is observed, in contrast to Au(12)(-) which is the critical size for the 2D-3D structural transition with both the 2D and 3D isomers coexisting. The current work shows that structural perturbations due to even isoelectronic substitution of a single Au atom shift the 2D to 3D structural transition of gold clusters to a smaller size.

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Section: Theoretical Results and Discussionmentioning

confidence: 64%

Section: Theoretical Methodsmentioning

confidence: 99%

Observation of earlier two-to-three dimensional structural transition in gold cluster anions by isoelectronic substitution: MAun− (n=8–11; M=Ag,Cu)

Wang

Pal

Huang

et al. 2010

The Journal of Chemical Physics

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“…Nevertheless, a definitive proof on the existence of an HGC conformation with more than 20 atoms remained elusive, particularly, among charged gold clusters. Among the neutral clusters, two HGC conformations, viz., Au 18 and Au 32 are widely studied for their potential electronic and catalytic properties [35][36][37][38][39][40]. These studies validate that both the HGCs are excellent red-ox agents and can be even an eminent choice for the selective oxidation of styrene to benzaldehyde [37].…”

Section: Introductionmentioning

confidence: 88%

Behaviour of ‘free-standing’ hollow Au nanocages at finite temperatures: a BOMD study

Joshi

Krishnamurty

2015

Molecular Physics

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Finite-temperature behaviour of a hollow golden cage (HGC) plays a crucialrole in its potential applications as a catalyst, drug delivery agent, contrasting agent and so on. This physico-chemical property of HGCs is not well understood so far. In that context, Born-Oppenheimer molecular dynamics (BOMD) simulations are performed on a well-known 'free-standing' HGC. The cluster considered in this study is the ground state Au 18 cluster (a cage with a diameter of about >5.5Å).The results thus obtained are compared with the BOMD simulation results reported earlier on Au 32 icosahedron cage, a conformation with a diameter of nearly. The sphericity of both the clusters is studied using a shape deformation parameter as a function of time and temperature. These results are supplemented by radial distribution function at various temperatures. The observations and analysis of results indicate that, both the clusters retain an HGC conformation from 300 to 400 K, admitting structural fluxionality by the Au 18 cluster. Remarkably, the Au 18 cluster is able to maintain its hollowness and sphericity up to a high temperature of 1000 K. Underlying structural and electronic properties influencing the individualistic behaviour of cages are highlighted. Composition of the frontier molecular orbitals and the charge distribution play a crucial role in the finite-temperature behaviour of the Au cages. The conclusions are supplemented by supporting calculations on another degenerate ground state Au 18 hollow cage and a well-known pyramidal Au 18 cage at 300 and 400 K.

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“…Because of the strong relativistic effects of the gold atom, the spin orbit (SO) coupling effect [74] also must be considered for heavy atoms such as gold. The PBE0/CRENBL level and SO effects were carefully selected for the gold atom to achieve quantitative agreement between the experimental and theoretical PES spectra [64,[75][76][77][78][79].…”

Section: Theoretical Methodsmentioning

confidence: 99%

Probing the structures and electronic properties of dual-phosphorus-doped gold cluster anions (AunP2-, n= 1–8): A density

Huang

Liu

et al. 2015

Chemical Physics

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a b s t r a c tThe geometries of gold clusters doped with two phosphorus atoms, Au n P À 2 (n = 1-8), were investigated using density functional theory (DFT) methods. Various two-dimensional (2D) and three-dimensional (3D) structures of the doped clusters were studied. The results indicate that the structures of dualphosphorus-doped gold clusters exhibit large differences from those of pure gold clusters with small cluster sizes. In our study, as for Au 6 P À 2 , two cis-trans isomers were found. The global minimum of Au 8 P À 2 presents a similar configuration to that of Au À 20 , a pyramid-shaped unit, and the potential novel optical and catalytic properties of this structure warrant further attention. The higher stability of Au n P À 2 clusters relative to Au À nþ2 (n = 1-8) clusters was verified based on various energy parameters, and the results indicate that the phosphorus atom can improve the stabilities of the gold clusters. We then explored the evolutionary path of Au n P À 2 (n = 1-8) clusters. We found that Au n P À 2 clusters exhibit the 2D-3D structural transition at n = 6, which is much clearer and faster than that of pure gold clusters and single-phosphorus-doped clusters. The electronic properties of Au n P À 2 (n = 1-8) were then investigated. The photoelectron spectra provide additional fundamental information on the structures and molecular orbitals shed light on the evolution of Au n P À 2 (n = 1-8). Natural bond orbital (NBO) described the charge distribution in stabilizing structures and revealed the strong relativistic effects of the gold atoms.

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CO chemisorption on the surfaces of the golden cages

Cited by 32 publications

References 64 publications

Observation of earlier two-to-three dimensional structural transition in gold cluster anions by isoelectronic substitution: MAun− (n=8–11; M=Ag,Cu)

Observation of earlier two-to-three dimensional structural transition in gold cluster anions by isoelectronic substitution: MAun− (n=8–11; M=Ag,Cu)

Behaviour of ‘free-standing’ hollow Au nanocages at finite temperatures: a BOMD study

Probing the structures and electronic properties of dual-phosphorus-doped gold cluster anions (AunP2-, n= 1–8): A density

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