Relativistic coupled cluster calculations for neutral and singly charged Au3 clusters

Wesendrup, Ralf; Hunt, Tricia; Schwerdtfeger, Peter

doi:10.1063/1.481556

Cited by 121 publications

(103 citation statements)

References 81 publications

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“…Once more, the relativistic effects are responsible for the larger values of the gold clusters. It is in accordance with the experimental data displayed in Figure 2 of Wesendrup et al 29 …”

Section: Stabilitysupporting

confidence: 81%

“…33,34 We would like to cite the experiments about vertical ionization potentials and electron affinities performed by some research groups, 28,[35][36][37][38][39] where the results of all studied gold clusters surpass those of the copper and silver ones (see Figure 2 of Wesendrup et al). 29 As a consequence of this finding, the properties and surfaces of the gold clusters will be differently affected. Thus, a study about the variation of such properties with the cluster size will be interesting.…”

Section: Introductionmentioning

confidence: 99%

“…Among the metal clusters, there is an increasing interest [20][21][22][23][24][25][26][27][28][29][30][31][32] in the noble metals (Cu, Ag, and Au) because they can be considered as a connection between the alkali metals and the transition metals. We recall that their electronic configurations are nd 10 (n + 1)s 1 , with n = 3, 4, and 5, respectively to Cu, Ag and Au.…”

Section: Introductionmentioning

confidence: 99%

“…As the central processing unit (CPU) time enhances rapidly with the cluster size, effective core potential (ECP) with a valence basis set has been extensively used to overcome difficulties. 27,[29][30][31][32] Another alternative is to employ relativistic density functional theory (DFT) along with an accurate allelectron basis set. To our knowledge, for the gold clusters, the latter strategy has not been used so far.…”

Section: Introductionmentioning

confidence: 99%

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Structures, Stabilities, Reactivities, and (Hyper)Polarizabilities of Small Gold Clusters

Jorge¹,

Santos²

2017

J. Braz. Chem. Soc.

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At the Douglas-Kroll-Hess level, the B3PW91 hybrid functional along with relativistic all-electron basis sets are used to evaluate geometric parameters, binding energies, vertical ionization potentials and electron affinities, and HOMO-LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital) energy gaps of the small golden clusters (Au n , n ≤ 8).The so expected odd-even oscillations of the experimental ionization potentials and electron affinities are confirmed in this work and the Au 7 cluster is predicted to be the most reactive cluster. Using the optimized geometries, DKH2 static mean dipole polarizability and polarizability anisotropy are also computed. From n ≥ 2, the mean dipole polarizabilities per atom present an odd-even oscillatory characteristic, whereas the polarizability anisotropies increase with the cluster size. At the non-relativistic level, the second hyperpolarizabilities are calculated. It is the first time that hyperpolarizabilities of gold clusters are reported. Comparisons with theoretical results obtained previously for the copper and silver clusters at the same level of theory are made.Keywords: B3PW91 functional, all-electron basis sets, DKH2 calculations, gold clusters, (hyper)polarizabilities IntroductionAtomic cluster is formed by an assembling of a few or hundreds of atoms. It is necessary to understand how the cluster properties vary with the size, to clarify how they evolve in the direction of the bulk properties. Metal clusters have received special attention in the literature due to their unusual characteristics, properties, and applications to build new electronic devices.1 Theoretical 2-11 and experimental [12][13][14][15][16][17][18][19] studies about metal clusters have been carried out for about thirty three years. Among the metal clusters, there is an increasing interest [20][21][22][23][24][25][26][27][28][29][30][31][32] in the noble metals (Cu, Ag, and Au) because they can be considered as a connection between the alkali metals and the transition metals. We recall that their electronic configurations are nd 10 (n + 1)s 1 , with n = 3, 4, and 5, respectively to Cu, Ag and Au. It has been verified that in general the gold clusters and compounds present large relativistic effects when compared to those of the copper and silver ones. 33,34 We would like to cite the experiments about vertical ionization potentials and electron affinities performed by some research groups, 28,[35][36][37][38][39] where the results of all studied gold clusters surpass those of the copper and silver ones (see Figure 2 of Wesendrup et al.). 29 As a consequence of this finding, the properties and surfaces of the gold clusters will be differently affected. Thus, a study about the variation of such properties with the cluster size will be interesting. In this article, the vertical ionization potentials and electron affinities of gold clusters with up to 8 atoms as well as binding energies, highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energ...

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“…Once more, the relativistic effects are responsible for the larger values of the gold clusters. It is in accordance with the experimental data displayed in Figure 2 of Wesendrup et al 29 …”

Section: Stabilitysupporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Structures, Stabilities, Reactivities, and (Hyper)Polarizabilities of Small Gold Clusters

Jorge¹,

Santos²

2017

J. Braz. Chem. Soc.

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“…The distorted Au 3 cluster has C 2v symmetry and two possible electronic states, 2 21 showed that even relativistic CCSD͑T͒ calculations with large basis sets predict the 2 A 1 state to be the ground state with the energy splitting between it and the 2 B 2 state of 4.4 kcal/mol. The same authors showed that relativistic MP2 calculations predict the 2 B 2 state to be 0.9 kcal/mol more stable than 2 A 1 .…”

Section: B Results For Aumentioning

confidence: 99%

The interaction of oxygen with small gold clusters

Varganov

Olson

Gordon

et al. 2003

The Journal of Chemical Physics

127

118

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Presented in this work are the results of a quantum chemical study of oxygen adsorption on small Aun and Au−n (n=2,3) clusters. Density functional theory(DFT), second order perturbation theory (MP2), and singles and doubles coupled clustertheory with perturbative triples [CCSD(T)] methods have been used to determine the geometry and the binding energy of oxygen to Aun. The multireference character of the wave functions has been studied using the complete active space self-consistent field method. There is considerable disagreement between the oxygen binding energies provided by CCSD(T) calculations and those obtained with DFT. The disagreement is often qualitative, with DFT predicting strong bonds where CCSD(T) predicts no bonds or structures that are bonded but have energies that exceed those of the separated components. The CCSD(T) results are consistent with experimental measurements, while DFT calculations show, at best, a qualitative agreement. Finally, the lack of a regular pattern in the size and the sign of the errors [as compared to CCSD(T)] is a disappointing feature of the DFT results for the present system: it is not possible to give a simple rule for correcting the DFT predictions (e.g., a useful rule would be that DFT predicts stronger binding of O2 by about 0.3 eV). It is likely that the errors in DFT appear not because of gold, but because oxygen binding to a metal cluster is a particularly difficult problem. Presented in this work are the results of a quantum chemical study of oxygen adsorption on small Au n and Au n Ϫ (nϭ2,3) clusters. Density functional theory ͑DFT͒, second order perturbation theory ͑MP2͒, and singles and doubles coupled cluster theory with perturbative triples ͓CCSD͑T͔͒ methods have been used to determine the geometry and the binding energy of oxygen to Au n . The multireference character of the wave functions has been studied using the complete active space self-consistent field method. There is considerable disagreement between the oxygen binding energies provided by CCSD͑T͒ calculations and those obtained with DFT. The disagreement is often qualitative, with DFT predicting strong bonds where CCSD͑T͒ predicts no bonds or structures that are bonded but have energies that exceed those of the separated components. The CCSD͑T͒ results are consistent with experimental measurements, while DFT calculations show, at best, a qualitative agreement. Finally, the lack of a regular pattern in the size and the sign of the errors ͓as compared to CCSD͑T͔͒ is a disappointing feature of the DFT results for the present system: it is not possible to give a simple rule for correcting the DFT predictions ͑e.g., a useful rule would be that DFT predicts stronger binding of O 2 by about 0.3 eV͒. It is likely that the errors in DFT appear not because of gold, but because oxygen binding to a metal cluster is a particularly difficult problem.

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Theoretical Chemistry of Gold – From Atoms to Molecules, Clusters, Surfaces and the Solid State

Schwerdtfeger

Lein

2009

Gold Chemistry

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Relativistic coupled cluster calculations for neutral and singly charged Au3 clusters

Cited by 121 publications

References 81 publications

Structures, Stabilities, Reactivities, and (Hyper)Polarizabilities of Small Gold Clusters

Structures, Stabilities, Reactivities, and (Hyper)Polarizabilities of Small Gold Clusters

The interaction of oxygen with small gold clusters

Theoretical Chemistry of Gold – From Atoms to Molecules, Clusters, Surfaces and the Solid State

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