Density Functional Theory Assessment of Molecular Structures and Energies of Neutral and Anionic Aln (n = 2–10) Clusters

Paranthaman, Selvarengan; Hong, Kiryong; Kim, Joonghan; Kim, Dong Eon; Kim, Tae Kyu

doi:10.1021/jp4074398

Cited by 45 publications

(46 citation statements)

References 60 publications

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“…The molecular structures of an isolated

{Al}_{7}^{-}

cluster, O 2 , and reaction products were optimized using M06‐2X, TPSSh, (hybrid‐meta functionals), and N12‐SX (range‐separated hybrid nonseparable gradient approximation (NGA)) with the all‐electron 6‐311+G(d) basis set. Both M06‐2X and TPSSh gave reasonable results that agree with previous experimental and high‐level theoretical data of Al clusters . B3LYP method was also used for the comparison with previous studies on the reaction of O 2 with Al clusters .…”

Section: Computational Detailssupporting

confidence: 81%

Reactivity of molecular oxygen with aluminum clusters: Density functional and Ab Initio molecular dynamics simulation study

Paranthaman

Moon

Hong

et al. 2016

Int J of Quantum Chemistry

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Dissociative adsorption of molecular oxygen (O 2 ) on aluminum (Al) clusters has attracted much interest in the field of surface science and catalysis, but theoretical predictions of the reactivity of this reaction in terms of barrier height is still challenging. In this regard, we systematically investigate the reactivity of O 2 with Al clusters using density functional theory (DFT) and atom-centered density matrix propagation (ADMP) simulations. We also calculate potential energy surfaces (PESs) of the reaction between O 2 and Al clusters to estimate the barrier energy of this reaction. The M06-2X functional gives the barrier energy in agreement with the one calculated by coupled cluster singles and doubles with perturbed triples (CCSD(T)) while the TPSSh functional significantly underestimates the barrier height. The ADMP simulation using the M06-2X functional predicts the reactivity of O 2 with the Al cluster in agreement with the experimental findings, that is, singlet O 2 readily reacts with Al clusters but triplet O 2 is less reactive. We found that the ability of a DFT functional to describe the charge transfer appropriately is critical for calculating the barrier energy and the reactivity of the reaction of O 2 with Al clusters. The M06-2X functional is relevant for investigating chemical reactions involving Al and O 2 .

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“…The molecular structures of an isolated

{Al}_{7}^{-}

Section: Computational Detailssupporting

confidence: 81%

Reactivity of molecular oxygen with aluminum clusters: Density functional and Ab Initio molecular dynamics simulation study

Paranthaman

Moon

Hong

et al. 2016

Int J of Quantum Chemistry

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“…So the Al 4 Si 2 demonstrates specific stability. Previous studies also revealed that Al 4 Si 4 , Al 8 Si, Al 8 Mg 2 , and

{Al}_{9}^{-}

clusters having 28 valence electrons show large energy gaps and enhanced stabilities . These clusters have similar oblate structures and their specific stabilities are interpreted by crystal field‐like splitting of the degenerate shells.…”

Section: Resultsmentioning

confidence: 89%

“…[40][41][42]55 Their lowest energy isomers are illustrated in Previous studies also revealed that Al 4 Si 4 , Al 8 Si, Al 8 Mg 2 , and Al − 9 clusters having 28 valence electrons show large energy gaps and enhanced stabilities. 42,43,56 These clusters have similar oblate structures and their specific stabilities are interpreted by crystal field-like splitting of the degenerate shells. Figure 2 Part of the stable adsorption systems is presented in Figure 3.…”

Section: Methodsmentioning

confidence: 99%

Adsorption and dissociation of H₂ on Al₄Si_m (m = 2, 3, and 4) clusters

Chen

2019

Env Prog and Sustain Energy

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Hydrogen in alanates forms AlH4− unit and the bonding strength depends on the electron donor property of the metal atoms. The electronic structures of Al─Si clusters are similar to metal clusters but the Al atom is a weaker electron donor than that in light metal alanates, so hydrogen may form weaker Al─H bonds in Al─Si systems. This article studies the adsorption and dissociation of H2 on Al4Si m (m = 2, 3, and 4) clusters by using density functional theory. The physisorption of H2 molecules on Al4Si m is very weak, the average binding energies of two H atoms on Al4Si m fall in the range –0.61 to –1.50 eV. It suggests that Al─Si hydrides can be candidates for hydrogen storage at ambient conditions. The investigation on the H2 dissociation processes shows that the lowest energy barrier is 0.76 eV, which implies that H2 dissociation can occur at moderate temperatures.

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“…[33], Al-Au [34,35], and Pd [1] clusters. According to this figure, Al 6 and Al 13 have the maximum hardness while Al 2 and Al 9 have the minimum hardness.…”

Section: Resultsmentioning

confidence: 99%

Theoretical study of geometry, stability and properties of Al and AlSi nanoclusters

Arab

Habibzadeh

2016

J Nanostruct Chem

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Geometry, stability, and properties of Al n (n = 1-13) and Al n Si m (n ? m = 5-7) nanoclusters were investigated by density functional theory. We found that while geometry of some clusters change significantly by substituting of Al atom(s) with Si atom(s) the geometry of some others remain without significant variation. The relative stability of clusters was discussed on the basis of binding energy per atom, fragmentation energy, and second-order difference of cluster energies. Our results reveal that Al 7 is the most stable cluster among pure clusters. For Al n Si m clusters, it is observed that Al 2 Si 3 (60 % Si), and Al 4 Si 2 (33.33 % Si) are the most stable clusters. The reactivity of Al n and Al n Si m nanoclusters was also investigated on the basis of chemical hardness. The most important feature of chemical hardness is its oscillating behavior as a function of atomic percentage of Si indicating that the reactivity of Al n Si m clusters strongly depends on the composition of cluster.

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Density Functional Theory Assessment of Molecular Structures and Energies of Neutral and Anionic Al_n (n = 2–10) Clusters

Cited by 45 publications

References 60 publications

Reactivity of molecular oxygen with aluminum clusters: Density functional and Ab Initio molecular dynamics simulation study

Reactivity of molecular oxygen with aluminum clusters: Density functional and Ab Initio molecular dynamics simulation study

Adsorption and dissociation of H₂ on Al₄Si_m (m = 2, 3, and 4) clusters

Theoretical study of geometry, stability and properties of Al and AlSi nanoclusters

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Density Functional Theory Assessment of Molecular Structures and Energies of Neutral and Anionic Aln (n = 2–10) Clusters

Cited by 45 publications

References 60 publications

Reactivity of molecular oxygen with aluminum clusters: Density functional and Ab Initio molecular dynamics simulation study

Reactivity of molecular oxygen with aluminum clusters: Density functional and Ab Initio molecular dynamics simulation study

Adsorption and dissociation of H2 on Al4Sim (m = 2, 3, and 4) clusters

Theoretical study of geometry, stability and properties of Al and AlSi nanoclusters

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Density Functional Theory Assessment of Molecular Structures and Energies of Neutral and Anionic Al_n (n = 2–10) Clusters

Adsorption and dissociation of H₂ on Al₄Si_m (m = 2, 3, and 4) clusters