Geometrical Structures of Partially Oxidized Rhodium Cluster Cations, Rh6Om+ (m = 4, 5, 6), Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Koyama, Kohei; Nagata, Toshiaki; Kudoh, Shinzoh; Miyajima, Ken; Huitema, Douwe M. M.; Chernyy, Valeriy; Bakker, Joost M.; Mafuné, Fumitaka

doi:10.1021/acs.jpca.6b08822

Cited by 13 publications

(20 citation statements)

References 37 publications

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“…Because the Ar atoms are weakly bound (typical binding energy calculated: ∼0.1 eV), they do not significantly affect the geometrical structures of the clusters, as is also evidenced by DFT calculations. Thus, the vibrational spectra of the clusters, Rh 7 O m + , can be obtained via IRMPD of their Ar-tagged complexes …”

Section: Resultsmentioning

confidence: 99%

“…The geometrical structures of Rh 7 O m + ( m = 4–7, 12, 14) were studied by IRMPD spectroscopy using a molecular beam-based experimental apparatus coupled to the free-electron laser for infrared experiments (FELIX). − Gas-phase Rh n O m + cluster ions were generated by laser ablation of a rhodium rod (99.9%) in a 4 mm diameter channel for cluster growth. The channel was filled with He carrier gas seeded with 0.016% oxygen introduced through a pulsed valve at a total stagnation pressure of 0.7 MPa.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…The laser ablation was performed using the focused 532 nm light from a pulsed Nd:YAG laser with a typical pulse energy of 25 mJ. Ar-attached clusters, Rh n O m Ar p + , were formed by mixing 0.6% argon gas in the carrier gas and cooling the cluster growth channel to about 200 K using liquid N 2 . The temperature was probed by a thermocouple and kept constant to within 1 K using a resistive heater and an electronic feedback circuit.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…In a previous study, we carried out further analysis of the fate of the remaining O atoms. For this purpose, we measured the vibrational spectra of Rh 6 O m + clusters using infrared multiple photon dissociation (IRMPD) spectroscopy and determined their geometrical structures by comparing these spectra with those calculated for optimized stable isomers using density functional theory (DFT) . It was concluded that Rh 6 O 4 + has a capped-square pyramidal Rh geometry with three bridging O atoms and one O atom in a hollow site and that Rh 6 O 5 + exhibits a prismatic Rh geometry with three bridging O atoms and two O atoms in hollow sites.…”

Section: Introductionmentioning

confidence: 99%

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Structures of Rhodium Oxide Cluster Cations Rh₇O_m⁺ (m = 4–7, 12, 14) Revealed by Infrared Multiple Photon Dissociation Spectroscopy

et al. 2019

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Vibrational spectra of Rh 7 O m + (m = 4−7, 12, 14) were measured in the 300−1300 cm −1 range via infrared multiple photon dissociation (IRMPD) spectroscopy. For the oxygen poor cluster sizes, Rh 7 O m + (m = 4−7), IRMPD spectra were recorded through photodissociation of Rh 7 O m + −Ar complexes. IR spectra for Rh 7 O m + (m = 12, 14) were recorded via the release of an O 2 molecule from Rh 7 O m + producing Rh 7 O m−2 + ; no O 2 loss was observed from Rh 7 O m + (m = 4−7, 8, 10). By comparison with the calculated vibrational spectra of several stable isomers obtained using density functional theory, these IR spectra are assigned to geometrical structures. For m = 4−7, all O atoms are bound to Rh atoms only, with a transition of the Rh core from capped octahedral to capped prismatic between m = 5 and m = 6. For the oxygen-rich Rh 7 O 12 + and Rh 7 O 14 + , molecular O 2 is adsorbed on a bridge site between two Rh atoms. The frequencies of the bands observed bands signal that the O 2 molecules are activated, indicating that rhodium oxide clusters with Rh 2 O 3 composition are still capable to donate electrons to activate O−O bonds in adsorbed O 2 .

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Section: Resultsmentioning

confidence: 99%

Section: Experimental Methodsmentioning

confidence: 99%

Section: Experimental Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structures of Rhodium Oxide Cluster Cations Rh₇O_m⁺ (m = 4–7, 12, 14) Revealed by Infrared Multiple Photon Dissociation Spectroscopy

et al. 2019

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“…The above comparison indicates that the O atoms in Ir 5 O m – prefer on-top binding motifs rather than bridging binding motifs throughout m = 1–8. The on-top binding motifs are in sharp contrast to the μ 2 or μ 3 binding modes on other transition metal clusters. − ,− This novel binding motif is understood by considering the shape of the frontier orbitals of the clusters involved in the bonding. Figure S5 compares the HOMO of the optimized structures of Ir 5 – and Co 5 – with the same spin multiplicity (13tet).…”

Section: Resultsmentioning

confidence: 99%

Structural Evolution of Iridium Oxide Cluster Anions Ir_nO_m^– (n = 5–8) with Sequential Oxidation: Binding Mode of O Atoms and Ir Framework

et al. 2019

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Geometric structures of small cluster anions of iridium oxide Ir n O m – (n = 5–8, m = 0–14) were investigated by ion mobility mass spectrometry (IMMS) and theoretical calculation to clarify the evolutional behavior of the binding modes of the O atoms and the motif of the Ir frameworks as a function of m. The collision cross sections (CCSs) for n = 5–7 determined by IMMS showed a monotonic increase with m, whereas those for n = 8 dropped abruptly by ∼10% at m = 11, which otherwise gradually increased with m. For n = 5, detailed comparison between the experimental CCS values and those calculated for various structural isomers revealed that the O atoms in Ir5O m – are preferentially bonded to terminal sites of the Ir5 – cores throughout m = 1–8: the Ir5 – cores retained compact motifs up to m = 5 but distorted significantly for m = 6–8. The experimental CCS values for Ir6O6 – and Ir7O7 – were also explained by on-top binding of O atoms while retaining the motifs of the Ir frameworks. The CCS values for n = 8 suggest that the O atoms are sequentially bonded to terminal sites of the cubic Ir8 frameworks for m = 1–6 and of the deformed Ir8 frameworks for m = 7–11. These on-top binding modes of the O atoms on small Ir clusters are in sharp contrast to the μ2 mode of the O atoms at bridge sites on the clusters of other transition metals and are ascribed to non-face-centered cubic (fcc) Ir frameworks. The sudden drop in the CCS values of Ir8O m – at m = 11 was associated with bond breakage in the Ir framework induced by transition of the binding mode of O atoms from an on-top motif to a μ2 bridging motif. These results suggest that the small Ir clusters exhibit novel oxidation catalysis by taking advantage of the unique chemical properties of O atoms adsorbed on the on-top sites on non-fcc Ir clusters.

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Infrared Multiphoton Dissociation Spectroscopy with Free‐Electron Lasers: On the Road from Small Molecules to Biomolecules

Jašíková

Roithová

2018

Chemistry A European J

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Infrared multiphoton dissociation (IRMPD) spectroscopy is commonly used to determine the structure of isolated, mass-selected ions in the gas phase. This method has been widely used since it became available at free-electron laser (FEL) user facilities. Thus, in this Minireview, we examine the use of IRMPD/FEL spectroscopy for investigating ions derived from small molecules, metal complexes, organometallic compounds and biorelevant ions. Furthermore, we outline new applications of IRMPD spectroscopy to study biomolecules.

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Geometrical Structures of Partially Oxidized Rhodium Cluster Cations, Rh₆O_m⁺ (m = 4, 5, 6), Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Cited by 13 publications

References 37 publications

Structures of Rhodium Oxide Cluster Cations Rh₇O_m⁺ (m = 4–7, 12, 14) Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Structures of Rhodium Oxide Cluster Cations Rh₇O_m⁺ (m = 4–7, 12, 14) Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Structural Evolution of Iridium Oxide Cluster Anions Ir_nO_m^– (n = 5–8) with Sequential Oxidation: Binding Mode of O Atoms and Ir Framework

Infrared Multiphoton Dissociation Spectroscopy with Free‐Electron Lasers: On the Road from Small Molecules to Biomolecules

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Geometrical Structures of Partially Oxidized Rhodium Cluster Cations, Rh6Om+ (m = 4, 5, 6), Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Cited by 13 publications

References 37 publications

Structures of Rhodium Oxide Cluster Cations Rh7Om+ (m = 4–7, 12, 14) Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Structures of Rhodium Oxide Cluster Cations Rh7Om+ (m = 4–7, 12, 14) Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Structural Evolution of Iridium Oxide Cluster Anions IrnOm– (n = 5–8) with Sequential Oxidation: Binding Mode of O Atoms and Ir Framework

Infrared Multiphoton Dissociation Spectroscopy with Free‐Electron Lasers: On the Road from Small Molecules to Biomolecules

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Geometrical Structures of Partially Oxidized Rhodium Cluster Cations, Rh₆O_m⁺ (m = 4, 5, 6), Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Structures of Rhodium Oxide Cluster Cations Rh₇O_m⁺ (m = 4–7, 12, 14) Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Structures of Rhodium Oxide Cluster Cations Rh₇O_m⁺ (m = 4–7, 12, 14) Revealed by Infrared Multiple Photon Dissociation Spectroscopy

Structural Evolution of Iridium Oxide Cluster Anions Ir_nO_m^– (n = 5–8) with Sequential Oxidation: Binding Mode of O Atoms and Ir Framework