Probing the structures of gas-phase rhodium cluster cations by far-infrared spectroscopy

Harding, Dan J.; Gruene, Philipp; Haertelt, Marko; Meijer, Gerard; Fielicke, André; Hamilton, Suzanne M.; Hopkins, W. Scott; Mackenzie, Stuart R.; Neville, Simon P.; Walsh, Tiffany R.

doi:10.1063/1.3509778

Cited by 76 publications

(130 citation statements)

References 63 publications

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“…This finding is consistent with recent screened hybrid-DFT calculations reported for Rh 13 , 27 which identified that an increase in the amount of exact Fock exchange in the hybrid functionals favors compact structures for Rh 13 , and hence, in better agreement with vibrational data. 24,25 However, it has been reported that low coordinated Rh n structures obtained by plain DFT calculations yield magnetic moments m T , in good agreement with experimental results. 10,[12][13][14][15][16] For example, plain DFT yields m T = 0.69 μ B /atom for Rh 13 , while results have obtained 0.48 ± 0.13 μ B /atom, 10 however, hybrid-DFT calculations yield higher magnetic moments for compact Rh n clusters (i.e., m T = 1.62 μ B /atom for Rh 13 ).…”

Section: Introductionsupporting

confidence: 75%

“…Thus, hybrid-DFT calculations yield compact structures and vibrational spectra in better agreement with experimental results, 24,25 however, the magnetic moments are too high compared with the experimental results. 10,27 In contrast, plain DFT yields open structures, which does not explain the vibrational spectra, 24,25 however, it yields total magnetic moments in excellent agreement with experimental results.…”

Section: Introductionsupporting

confidence: 60%

“…Most of the studies have addressed the atomic structure of Rh n as a function of size, [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27] the vibrational spectra, 24,25,28 magnetic moments, 3,10,12,14,16,18,22 polarizabilities, 16,29 and the catalytic activity for small molecules. 21,[30][31][32][33][34] Among those studies, hybrid-DFT calculations combined with experimental far-infrared multiple photon dissociation 24,25 have reported that Rh + n clusters have compact structures based on octahedron motifs for n = 6-12 (i.e., only compact structures can explain the vibrational spectra). This finding is consistent with recent screened hybrid-DFT calculations reported for Rh 13 , 27 which identified that an increase in the amount of exact Fock exchange in the hybrid functionals favors compact structures for Rh 13 , and hence, in better agreement with vibrational data.…”

Section: Introductionmentioning

confidence: 99%

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Hybrid density functional study of small Rhn(n=2−15)clusters

2012

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The physical properties of small rhodium clusters, Rh n , have been in debate due to the shortcomings of density functional theory (DFT). To help in the solution of those problems, we obtained a set of putative lowest energy structures for small Rh n (n = 2-15) clusters employing hybrid-DFT and the generalized gradient approximation (GGA). For n = 2-6, both hybrid and GGA functionals yield similar ground-state structures (compact), however, hybrid favors compact structures for n = 7-15, while GGA favors open structures based on simple cubic motifs. Thus, experimental results are crucial to indicate the correct ground-state structures, however, we found that a unique set of structures (compact or open) is unable to explain all available experimental data. For example, the GGA structures (open) yield total magnetic moments in excellent agreement with experimental data, while hybrid structures (compact) have larger magnetic moments compared with experiments due to the increased localization of the 4d states. Thus, we would conclude that GGA provides a better description of the Rh n clusters, however, a recent experimental-theoretical study [Harding et al., J. Chem. Phys. 133, 214304 (2010)] found that only compact structures are able to explain experimental vibrational data, while open structures cannot. Therefore, it indicates that the study of Rh n clusters is a challenging problem and further experimental studies are required to help in the solution of this conundrum, as well as a better description of the exchange and correlation effects on the Rh n clusters using theoretical methods such as the quantum Monte Carlo method.

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Section: Introductionsupporting

confidence: 75%

Section: Introductionsupporting

confidence: 60%

Section: Introductionmentioning

confidence: 99%

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Hybrid density functional study of small Rhn(n=2−15)clusters

2012

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“…A similar study, combining IR-MPD with BH-DFT calculations, was presented by Walsh and coworkers for Rh 1 N (N56212). [170,171] They observed a significant dependence of the most stable putative GM and its spin multiplicity on the functional, making the identification of the geometric and electronic GM very challenging. [170] These case studies illustrate the problems FP-GOs face when investigating transition metal clusters using DFT methods.…”

Section: Basin Hoppingmentioning

confidence: 99%

Global optimization of clusters using electronic structure methods

Heiles

Johnston

2013

Int J of Quantum Chemistry

197

191

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Over the past decade, there has been a significant growth in the development and application of methods for performing global optimization (GO) of cluster and nanoparticle structures using first-principles electronic structure methods coupled to sophisticated search algorithms. This has in part been driven by the desire to avoid the use of empirical potentials (EPs), especially in cases where no reliable potentials exist to guide the search toward reasonable regions of configuration space. This has been facilitated by improvements in the reliability of the search algorithms, increased efficiency of the electronic structure methods, and the development of faster, multiprocessor high-performance computing architectures. In this review, we give a brief overview of GO algorithms, though concentrating mainly on genetic algorithm and basin hopping techniques, first in combination with EPs. The major part of the review then deals with details of the implementation and application of these search methods to allow exploration for global minimum cluster structures directly using electronic structure methods and, in particular, density functional theory. Example applications are presented, ranging from isolated monometallic and bimetallic clusters to molecular clusters and ligated and surface supported metal clusters. Finally, some possible future developments are highlighted.

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“…A better understanding of the nature of these fundamental interactions would inform fields as diverse as molecule surface interactions [1] and buffer gas cooling. [2] The study of such molecules has been lent added impetus in recent years, by the popular use of rare gas atoms as messenger tags in action spectroscopy studies of gas-phase metal-ligand [3,4] naked metal [5][6][7][8] and metal oxide clusters. [9][10][11] In such studies, the structures of interest are widely assumed to be affected minimally by the presence of the inert tag with the result that the photodissociation action spectrum mirrors that of the naked species.…”

Section: Introductionmentioning

confidence: 99%

Dissociation energies of Ag–RG (RG = Ar, Kr, Xe) and AgO molecules from velocity map imaging studies

Cooper¹,

Kartouzian

Gentleman³

et al. 2015

The Journal of Chemical Physics

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The near ultraviolet photodissociation dynamics of silver atom -rare gas dimers have been studied by velocity map imaging. Ag-RG (RG = Ar, Kr, Xe) species generated by laser ablation are excited in the region of the C ( 2  + )  X ( 2  + ) continuum leading to direct, near-threshold dissociation generating Ag* ( 2 P 3/2 ) + RG ( 1 S 0 ) products. Images recorded at excitation wavelengths throughout the C ( 2  + )  X ( 2  + ) continuum, coupled with known atomic energy levels, permit determination of the ground X ( 2  + ) state dissociation energies of 85.9 ± 23.4 cm -1 (Ag-Ar), 149.3 ± 22.4 cm -1 (Ag-Kr) and 256.3 ± 16.0 cm -1 (Ag-Xe). Three additional photolysis processes, each yielding Ag atom photoproducts, are observed in the same spectral region. Two of these are markedly enhanced in intensity upon seeding the molecular beam with nitrous oxide, and are assigned to photodissociation of AgO at the two-photon level. These features yield an improved ground state dissociation energy for AgO of 15965  81 cm -1 , which is in good agreement with high level calculations. The third process results in Ag atom fragments whose kinetic energy shows anomalously weak photon energy dependence and is assigned tentatively to dissociative ionization of the silver dimer Ag 2 .3

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Probing the structures of gas-phase rhodium cluster cations by far-infrared spectroscopy

Cited by 76 publications

References 63 publications

Hybrid density functional study of small Rhn(n=2−15)clusters

Hybrid density functional study of small Rhn(n=2−15)clusters

Global optimization of clusters using electronic structure methods

Dissociation energies of Ag–RG (RG = Ar, Kr, Xe) and AgO molecules from velocity map imaging studies

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