Melting Dramatically Enhances the Reactivity of Aluminum Nanoclusters

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

doi:10.1021/ja809516h

Cited by 56 publications

(66 citation statements)

References 18 publications

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“…They have been studied in a series of experimental and the oretical works (see, for example, [4][5][6][7] and references Abstract-Segments of the potential energy surfaces corresponding to successive elementary stages of mul tistep fragmentation of nitrogen and diimine molecules upon their reaction with the aluminum cluster Al 13 and its doped analogue Al 12 Ti have been calculated by the density functional theory method. The minimum energy pathways of these reactions have been calculated for the stages of physisorption, chemisorption, and N 2 and N 2 H 2 fragmentation with different ways of insertion of fragments into the Al 13 and Al 12 Ti cages.…”

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Theoretical study of isomerism of compounds of N2 and N2H2 molecules with aluminum clusters Al13 and Al12Ti

Чаркин

2014

Russ. J. Inorg. Chem.

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Previously [1-3], we have studied isomers and intramolecular rearrangements involving the addition, activation, and subsequent fragmentation of mole cules with multiple bonds upon their reaction with aluminum clusters doped with 3d transition atoms. We performed density functional theory (DFT) calcula tions of the potential energy surfaces (PES) along the minimum energy pathways (MEPs) of "sorption" stages of formation of Al 12 Тi(π L) complexes with L molecules containing multiple bonds (L = С 2 Н 2 , С 2 Н 4 , N 2 Н 2 , НСN, С 6 Н 6 , С 60 , СО 2 , etc.) side on coordinated (π type or η 2 coordination) to the tita nium atom located at the top of the titanium doped aluminum cluster with 12 vertices and a centered mar quee structure [1], as well as DFT calculations of acet ylene analogues like Al 12 МС 2 Н 2 with different 3d tran sition metal dopants M [2]. For the latter, we have considered the activation and fragmentation stages of isomerization (after sorption) related to different channels of dissociation of the С 2 Н 2 into CH + CH, H + С 2 Н, or H + H + C + C fragments to form more favorable fragment isomers of the same composition Al 12 МС 2 Н 2 but in which acetylene dissociation frag ments are differently built into the marquee aluminide cage Al 12 М and augment it to the Al 12 МС 2 carbalu minide cage with 14 vertices. In [3], analogous calcu lations have been performed for the Al 12 Тi and Al 12 Ni complexes with CO and СО 2 molecules. For most compounds, three types of low lying isomers have been localized. In one of them, the strongly polarized C 2 H 2 molecule can be coordinated to the M dopant, to an M-Al edge, or a MAl 2 trigonal face of the metal cage; in the second isomer, both diatomic CH frag ments are in capping positions over adjacent MAl 2 faces; the third isomer contains a five coordinate C* atom with a pyramidal environment located near the centers of quasi planar tetragonal MAl 3 faces and bound to the central Al c atom through the fifth bond. An unusual isomer has been localized in which both carbon atoms are built into the aluminum cage as five coordinate C* atoms. A specific feature of the isomers containing five coordinate carbon is that the C* atom in them is able to add, with a considerable decrease in total energy, acceptor BH 3 or AlH 3 ligands and to increase its coordination number to six (six coordi nate carbon) in Al 12 MC 2 H 2 BH 3 complexes.This work is a continuation of our studies [1-3] and deals with quantum chemical modeling of isom erism in Al 12 M + N 2 and Al 12 M + N 2 H 2 complex sys tems (M = Al, Ti) in which the metal clusters Al 13 and Al 12 Ti are bound to the N 2 and N 2 Н 2 molecules. The choice of objects for study was motivated by the fol lowing reasons.The interactions of metal clusters with the N 2 mol ecule ae of interest for understanding the mechanisms of activation and fixation of molecular nitrogen. They have been studied in a series of experimental and the oretical works (see, for example, [4][5][6][7] and references Abstract-Segments of the poten...

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“…They have been studied in a series of experimental and the oretical works (see, for example, [4][5][6][7] and references therein). A theoretical study of the reaction of N 2 with the perfect (111) surface of solid aluminum [4] has demonstrated that the reaction is highly exothermic and has a high activation barrier of ~3 eV.…”

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confidence: 99%

Theoretical study of isomerism of compounds of N2 and N2H2 molecules with aluminum clusters Al13 and Al12Ti

Чаркин

2014

Russ. J. Inorg. Chem.

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“…Calculations considering a liquid surface of aluminum show activation energies from 290 kJ mol À1 for a perpendicular orientation to the surface of the N 2 molecule up to 308.8 kJ mol À1 for a parallel orientation [46]. Cao et al [47] state that a melted aluminum surface might lower the activation energy of the dissociative adsorption of nitrogen. Our calculated energy barrier is 336.7 kJ mol À1 which is consistent with the previous results mentioned.…”

Section: Nitrogen (N 2 ) and Hydrogen (H 2 )mentioning

confidence: 99%

Gas-surface thermochemistry and kinetics for aluminum particle combustion

Glorian¹,

Catoire²,

Gallier³

et al. 2015

Proceedings of the Combustion Institute

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“…For example, the investigation by Jarrold et al revealed that the reactivity of Al clusters can be enhanced through cluster melting; 19 Mottet et al found the melting points of Ag clusters can be changed by doping; 20 The correlations with structural changes are often investigated to explore the melting behaviors of metal clusters in detail. For example, the distinct isomerization transitions occurred prior to its full melting for a 38-atom Co cluster; 21 Schebarchov et al found there is a structural change from the icosahedron to the decahedron in liquid-solid co-existing Ni cluster; 22 Wen et al specifically studied the shape transformation of a tetrahedral Pt cluster during its melting.…”

Section: Introductionmentioning

confidence: 99%

Molecular dynamical simulations of melting behaviors of metal clusters

2015

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The melting behaviors of metal clusters are studied in a wide range by molecular dynamics simulations. The calculated results show that there are fluctuations in the heat capacity curves of some metal clusters due to the strong structural competition; For the 13-, 55-and 147-atom clusters, variations of the melting points with atomic number are almost the same; It is found that for different metal clusters the dynamical stabilities of the octahedral structures can be inferred in

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Melting Dramatically Enhances the Reactivity of Aluminum Nanoclusters

Cited by 56 publications

References 18 publications

Theoretical study of isomerism of compounds of N2 and N2H2 molecules with aluminum clusters Al13 and Al12Ti

Theoretical study of isomerism of compounds of N2 and N2H2 molecules with aluminum clusters Al13 and Al12Ti

Gas-surface thermochemistry and kinetics for aluminum particle combustion

Molecular dynamical simulations of melting behaviors of metal clusters

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