Reactions of liquid and solid aluminum clusters with N2: The role of structure and phase in Al114+, Al115+, and Al117+

Cao, Bangwei; Starace, Anthony F.; Judd, Oscar H.; Bhattacharyya, Indrani; Jarrold, Martin F.

doi:10.1063/1.4901895

Cited by 8 publications

(2 citation statements)

References 63 publications

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“…In this study, a key intermediate (Scheme c), with N 2 binding to three metal atoms in the end-on/side-on/side-on mode M 3 (μ 3 -η 1 :η 2 :η 2 -N 2 ), is suggested in the feasible NN bond cleavage by trinuclear vanadium carbide cluster anions by employing experimental techniques of mass spectrometry and cryogenic photoelectron imaging spectroscopy combined with high-level quantum chemistry calculations. Note that dinitrogen activation by gas-phase polynuclear metal clusters has been studied, while the vital intermediate shown as Scheme c for NN cleavage was not realized. − …”

Section: Introductionmentioning

confidence: 99%

A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V₃C₄^–

Mou

et al. 2020

J. Am. Chem. Soc.

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Cleavage of the triple NN bond by metal clusters is of fundamental interest and practical importance in nitrogen fixation. Previous studies of NN bond cleavage by gas-phase metal clusters emphasized the importance of the dinuclear metal centers. Herein, the dissociative adsorption of N2 and subsequent C–N coupling on trinuclear carbide cluster anions V3C4 – under thermal collision conditions have been characterized by employing mass spectrometry (collision induced dissociation), cryogenic photoelectron imaging spectroscopy, and quantum chemistry calculations. A theoretical analysis identified a crucial adsorption intermediate with N2 bonded with the V3 metal core in the end-on/side-on/side-on (ESS) mode, which most likely enables the facile cleavage of the NN bond. Such a vital N2 coordination in the ESS mode is a result of symmetry-matched interactions between the occupied orbitals of the metal core and both of the two empty π* orbitals of N2. Furthermore, carbon ligands also play a considerable role in enhancing the reactivity of the metal core toward N2. This study strongly suggests a new mechanism of NN bond cleavage by gas-phase metal clusters.

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Section: Introductionmentioning

confidence: 99%

A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V₃C₄^–

Mou

et al. 2020

J. Am. Chem. Soc.

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“…Aluminum clusters have been the subject of several studies where the reactivity of liquid and solid clusters was compared. For example, the chemisorption of N 2 has been studied both experimentally and through DFT and molecular dynamics simulations. − The kinetic energy thresholds for chemisorption of N 2 were lower for the liquid cluster than the solid cluster for Al 44 ± and Al 100 + , but not for Al 114 + , Al 115 + , and Al 117 + . Further differences in the chemistry of liquid aluminum clusters versus their solid counterparts were observed in the reactivity of CO 2 and benzene with Al 100 + . , …”

Section: Introductionmentioning

confidence: 99%

Melting of Size-Selected Aluminum Clusters with 150–342 Atoms: The Transition to Thermodynamic Scaling

2017

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Heat capacities have been measured by ion calorimetry for size-selected aluminum cluster cations ranging in size from 150 to 342 atoms. All clusters show a sharp peak in their heat capacity versus temperature plots which is attributed to the melting transition. The large size dependent fluctuations in the melting temperatures found for smaller clusters in previous work have largely vanished. The melting temperatures for the 150−342 atom size range examined here are substantially below the bulk value and increase relatively smoothly with size. Above 180 atoms, they closely follow the 1/r dependence predicted by thermodynamic models. A notable exception occurs between Al 283 + and Al 284 + , where the melting temperature suddenly jumps by 13 K. This jump represents a remarkably sudden change for such large clusters. The origin is probably structural, but the nature of the structural change remains unknown. The latent heat is still far from its bulk value (only 42%) even for the largest clusters studied here. When the data for aluminum clusters and particles are combined, melting temperatures are available over a size range spanning 6 decades, providing a complete picture of how the melting temperature changes with size.

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Design and Application of a High-Temperature Linear Ion Trap Reactor

Jiang

Liu

et al. 2017

J. Am. Soc. Mass Spectrom.

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A high-temperature linear ion trap reactor with hexapole design was homemade to study ion-molecule reactions at variable temperatures. The highest temperature for the trapped ions is up to 773 K, which is much higher than those in available reports. The reaction between VO cluster anions and CO at different temperatures was investigated to evaluate the performance of this reactor. The apparent activation energy was determined to be 0.10 ± 0.02 eV, which is consistent with the barrier of 0.12 eV calculated by density functional theory. This indicates that the current experimental apparatus is prospective to study ion-molecule reactions at variable temperatures, and more kinetic details can be obtained to have a better understanding of chemical reactions that have overall barriers. Graphical Abstract.

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Reactions of liquid and solid aluminum clusters with N2: The role of structure and phase in Al114+, Al115+, and Al117+

Cited by 8 publications

References 63 publications

A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V₃C₄^–

A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V₃C₄^–

Melting of Size-Selected Aluminum Clusters with 150–342 Atoms: The Transition to Thermodynamic Scaling

Design and Application of a High-Temperature Linear Ion Trap Reactor

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Reactions of liquid and solid aluminum clusters with N2: The role of structure and phase in Al114+, Al115+, and Al117+

Cited by 8 publications

References 63 publications

A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V3C4–

A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V3C4–

Melting of Size-Selected Aluminum Clusters with 150–342 Atoms: The Transition to Thermodynamic Scaling

Design and Application of a High-Temperature Linear Ion Trap Reactor

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Product

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A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V₃C₄^–

A Facile N≡N Bond Cleavage by the Trinuclear Metal Center in Vanadium Carbide Cluster Anions V₃C₄^–