A First Principles Study of Palladium Clusters in Gmelinite and Their Interaction with CO

and, Víctor Durà-Vilà; Gale, Julian D.

doi:10.1021/jp004219b

Cited by 13 publications

(12 citation statements)

References 54 publications

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“…The PdCO molecule has been considered in several theoretical studies. [25][26][27][28][29][30][31][32][33][34] The available experimental data include structural parameters obtained from the microwave spectrum 35 and vibrational frequencies. 27,[36][37][38] Table 1 shows CO binding energies (DE) and structural parameters obtained at different levels of theory in comparison to experiment.…”

Section: Pdco and Pd 2 Comentioning

confidence: 99%

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Effects of ligand coverage on properties of palladium clusters. A density functional theory study

Nava

Sierka

Ahlrichs

2004

Phys. Chem. Chem. Phys.

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International audienceLigand stabilized clusters of palladium are treated at density functional theory level to investigate effects of ligand coverage on properties, such as preferred coordination sites, metal–ligand binding energies, and structure. Systems investigated include cores of Pdn, for n = 1,2,13,16,19,23,35,39, stabilized by CO, PH3, and P(CH3)3, which are either known experimentally or have been proposed as intermediates in syntheses. Some of these systems, e.g. Pd13(CO)i, served as models to study aspects of ligand metal binding. The main results are the following. CO binds preferably as μ3 such that coordination sites share at most one vertex atom. The ligand coverage weakens Pd–Pd bonding and quenches the high spin of pure metal clusters. Ligands tend to stabilize Pd cores showing icosahedral Pd13 structural units such as biicosahedra in Pd19 and Pd23, whereas the corresponding bare metal clusters are most stable as octahedron and decahedron, respectively. The BP86 density functional yields reliable structure parameters and ligand metal binding energies in cases where comparison with experiment or accurate calculations is possible, only Pd(CO)i, i = 1–4, appears to be an exception

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Section: Pdco and Pd 2 Comentioning

confidence: 99%

“…This system has been previously studied at MRSDCI and DFT-PBE level. 26,39 In the most stable structure the CO ligand is located in a bridging m 2 position, as shown in Fig. 2a.…”

Section: Pdco and Pd 2 Comentioning

confidence: 99%

Effects of ligand coverage on properties of palladium clusters. A density functional theory study

Nava

Sierka

Ahlrichs

2004

Phys. Chem. Chem. Phys.

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“…2 The interactions within gas-phase PdCO are prototypes for those between a Pd surface and CO, and consequently, the PdCO molecule has been the subject of many theoretical studies. [3][4][5][6][7][8][9][10][11][12][13][14][15] The infrared spectrum of PdCO isolated in krypton was reported by Darling et al 16 in 1973. Following this work, many groups have applied theoretical methods to examine aspects of the electronic structure of PdCO.…”

Section: Introductionmentioning

confidence: 99%

Microwave Spectrum, Geometry, and Hyperfine Constants of PdCO

2002

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The pure rotational spectrum of palladium monocarbonyl, PdCO, has been measured between 6000 and 24 000 MHz using a cavity pulsed jet Fourier transform microwave spectrometer. The molecules were prepared by laser ablation of Pd in the presence of CO contained in an Ar backing gas. The spectra of 15 isotopomers have been used to determine the molecular geometry from the measured rotational constants. Centrifugal distortion constants are in good agreement with those calculated from a literature harmonic force field. A nuclear quadrupole coupling constant and nuclear spin-rotation constant have been determined for 105 Pd. Nuclear shielding parameters have been evaluated from the measured spin-rotation constant. The geometry is discussed with reference to theoretical data and to other molecules containing an M-CO bond.

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“…The more extensive use of SIESTA in this field is due to Gale and coworkers [144][145][146]. An illustrative example is the study of the binding of palladium atoms and dimers in the zeolite gmelinite.…”

Section: Minerals and Zeolitesmentioning

confidence: 99%