Direct IR Spectroscopic Detection of a Low‐Lying Electronic State in a Metal Carbide Cluster

Chernyy, Valeriy; Logemann, R.; Kirilyuk, Andrei; Bakker, Joost M.

doi:10.1002/cphc.201701365

Cited by 7 publications

(5 citation statements)

References 26 publications

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“…Our IRMPD technique is complementary to this method but sensitive to lower oscillator strengths -the C=O and C=S stretches in [Au10OCS] + , clearly observed in Figure 1(c) (and ref [62]) have oscillator strengths, f=2×10 -4 and 7×10 -6 , respectively [89]. This is not the first time that electronic states have been observed by IRMPD -Bakker and coworkers having reported low energy electronic bands in Ta5C3 [90].…”

Section: Figures 1(b)-(d)mentioning

confidence: 73%

Atomic Cluster Au10+ Is a Strong Broadband Midinfrared Chromophore

et al. 2021

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We report an intense broadband mid infrared absorption band in the Au10 + cluster in a region in which only molecular vibrations would normally be expected. Observed in the infrared multiple photon dissociation spectra of Au10Ar + , Au10(N2O) + and Au10(OCS) + , the smooth feature stretches 700-3400 cm -1 (=14-2.9 µm). Calculations confirm unusually low-energy allowed electronic excitations consistent with the observed spectra. In Au10(OCS) + , IR absorption throughout the band drives OCS decomposition resulting in CO loss, providing an alternative method of bond activation/breaking. TOC GRAPHICSAu10 + exhibits a remarkable, broad absorption feature in the mid infrared where only molecular vibrational bands would normally be expected.

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Section: Figures 1(b)-(d)mentioning

confidence: 73%

Atomic Cluster Au10+ Is a Strong Broadband Midinfrared Chromophore

et al. 2021

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“…Another could be an electronic transition between the vibrationless ground states of the 2A′ and 2A″ states, that according to the current calculations would lie at 1460/1742 cm –1 using the B3LYP/CCSD(T) energies. Although unusual, electronic transitions have been observed previously in IRMPD spectra of M 5 C 3 and cobalt clusters . We have no obvious explanation for the possible band at 1000 cm –1 .…”

Section: Resultsmentioning

confidence: 99%

Infrared Spectroscopic Characterization of Early 4d Transition Metal Carbene Cations, ZrCH₂⁺ and NbCH₂⁺

Armentrout,

Lushchikova,

Schuurman

et al. 2024

J. Phys. Chem. A

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IR multiple-photon dissociation (IRMPD) action spectroscopy is combined with quantum chemical calculations to examine the [M,C,2H] + species for the early 4d metals, M = Zr and Nb. These ions were formed by reacting laser ablated M + ions with cyclopropane (c-C 3 H 6 ) in a molecular beam apparatus. Both IRMPD spectra exhibit one major band near 700 cm −1 and a second weaker band at about twice that wavenumber, more evident when irradiated in focus. The [Nb,C,2H] + species also has a sharp band at 800 cm −1 . Comparison with B3LYP calculations allow assignment of the [M,C,2H] + structures to agostic carbenes, which is similar to the structures found for the 5d analogues, WCH 2 + and TaCH 2 + . A molecular orbital analysis traces the reasons for the agostic deformation from a classic C 2v symmetric carbene.

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“…A comparison between the calculated and experimental values of vibrational frequency is a sensitive benchmark for testing the performance of different computational models in order to judge their accuracy and to apply them to larger or more complex systems. 53,54 Thus, to obtain structural information and to distinguish those competitive candidates for the ground state that are nearly degenerate with an approximate energy, we hope that further experimental research on vibrational spectra will be performed in the future to compare with our theoretical spectra.…”

Section: Vibrational Spectramentioning

confidence: 99%

Probing the properties of size dependence and correlation for tantalum clusters: geometry, stability, vibrational spectra, magnetism, and electronic structure

Chen

Basnet

et al. 2019

RSC Adv.

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A comprehensive investigation on the equilibrium geometry, relative stability, vibrational spectra, and magnetic and electronic properties of neutral tantalum clusters (Ta n , n ¼ 2-17) was performed using density functional theory (DFT). We perform a study of the size dependence and correlations among those descriptors of parameters, and showed these could provide a novel way to confirm and predict experimental results. Some new isomer configurations that have never been reported before for tantalum clusters were found. The growth behaviors revealed that a compact geometrical growth route is preferred and develops a body-centered-cubic (BCC) structure with the cluster size increasing. The perfectly fitted functional curve, strong linear evolution, and obvious odd-even oscillation behavior proved their corresponding properties depended on the cluster size. Multiple demonstrations of the magic number were confirmed through the correlated relationships with the relative stability, including the second difference in energy, maximum hardness, and minimum polarizability. An inverse evolution trend between the energy gap and electric dipole moment and strong linear correlation between ionization potentials and polarizability indicated the strong correlation between the magnetic and electronic properties. Vibrational spectroscopy as a fingerprint was used to distinguish the ground state among the competitive geometrical isomers close in energy. The charge density difference isosurface, density of states, and molecular orbitals of selected representative clusters were analyzed to investigate the difference and evolutional trend of the relative stability and electronic structure. In addition, we first calculated the ionization potential and magnetic moment and compared these with the current available experimental data for tantalum clusters. † Electronic supplementary information (ESI) available: The computational details including DFT method, denition of reactivity descriptors, and nite eld treatment method; the analysis of geometrical isomers and their energy difference; the calculated parameters of neutral Ta n (n ¼ 2-17) clusters for all relative stable geometrical isomers (Table S1); the DOS of representative Ta n (n ¼ 7, 10, 13 and 15) clusters (Fig. S1). See

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Direct IR Spectroscopic Detection of a Low‐Lying Electronic State in a Metal Carbide Cluster

Cited by 7 publications

References 26 publications

Atomic Cluster Au10+ Is a Strong Broadband Midinfrared Chromophore

Atomic Cluster Au10+ Is a Strong Broadband Midinfrared Chromophore

Infrared Spectroscopic Characterization of Early 4d Transition Metal Carbene Cations, ZrCH₂⁺ and NbCH₂⁺

Probing the properties of size dependence and correlation for tantalum clusters: geometry, stability, vibrational spectra, magnetism, and electronic structure

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Direct IR Spectroscopic Detection of a Low‐Lying Electronic State in a Metal Carbide Cluster

Cited by 7 publications

References 26 publications

Atomic Cluster Au10+ Is a Strong Broadband Midinfrared Chromophore

Atomic Cluster Au10+ Is a Strong Broadband Midinfrared Chromophore

Infrared Spectroscopic Characterization of Early 4d Transition Metal Carbene Cations, ZrCH2+ and NbCH2+

Probing the properties of size dependence and correlation for tantalum clusters: geometry, stability, vibrational spectra, magnetism, and electronic structure

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Infrared Spectroscopic Characterization of Early 4d Transition Metal Carbene Cations, ZrCH₂⁺ and NbCH₂⁺