Theoretical prediction of atomic and electronic structure of neutral Si6Om (m=1–11) clusters

Caputo, M. C.; Oña, Ofelia B.; Ferraro, Marta B.

doi:10.1063/1.3080549

Cited by 10 publications

(20 citation statements)

References 49 publications

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“…The Si 6 O isomers are, however, most stable with an O atom on the edge of a low-energy isomer of the Si 6 cluster. Our numerical results are in good agreement with earlier calculations of Si 6 O 24 and Si 6 B. 51 Furthermore, to the best of our knowledge, we have found a new lowest-energy structure for the Si 6 N cluster (d0, Fig.…”

Section: A Predicted Structuressupporting

confidence: 91%

“…Whereas an enormous amount of theoretical work on small doped silicon clusters is available (e.g., ref. 12,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34], only a few experiments have been reported in the gas phase. 8,14,[35][36][37][38] By sequential doping of silicon clusters with carbon atoms, i.e., for Si m C n with m + n = 6, we recently observed a systematic transition from one-dimensional geometries for pure C 6 to three-dimensional structures for pure Si 6 .…”

Section: Introductionmentioning

confidence: 99%

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Vibrational spectra and structures of neutral Si₆X clusters (X = Be, B, C, N, O)

Trường

Savoca

Harding

et al. 2014

Phys. Chem. Chem. Phys.

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aNeutral silicon clusters doped with first row elements (Si 6 X) have been generated (X = B, C, N, O) and characterized by infrared-ultraviolet (IR-UV) two-photon resonance-enhanced ionization spectroscopy (X = C, O) and quantum chemical calculations (X = Be, B, C, N, O, Si). In the near threshold UV photoionization, the ion signal of specific cluster sizes can be significantly enhanced by resonant excitation with tunable IR light prior to UV irradiation, allowing for the measurement of the IR spectra of Si 7 , Si 6 C, and Si 6 O clusters.Structural assignments are achieved with the help of a global optimization procedure using density functional theory (DFT). The most stable calculated structures show the best agreement between predicted and measured spectra. The dopant atoms in the Si 6 X clusters have a negative net charge and the Si atoms act as electron donors within the clusters. Moreover, the overall structures of the Si 6 X clusters depend strongly on the nature of the dopant atom, i.e., its size and valency. While in some of the Si 6 X clusters one Si atom in Si 7 is simply substituted by the dopant atom (X = Be, B, C), other cases exhibit a completely different geometry (X = N, O). As a general trend, doping of the Si 7 cluster with first-row dopants is predicted to shift the optically allowed electronic transitions into the visible or even near-IR spectral range due to symmetry reduction or the radical character of the doped cluster.

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Section: A Predicted Structuressupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Vibrational spectra and structures of neutral Si₆X clusters (X = Be, B, C, N, O)

Trường

Savoca

Harding

et al. 2014

Phys. Chem. Chem. Phys.

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“…34,35 The energies of 10 best structures for each composition were refined using the GAUSSIAN code 36 with the B3LYP/6-311+G(2d,p) approach. 37 Comparison of our results with earlier publications 4,6,10,[26][27][28][30][31][32][33] showed that 101 optimal structures of Si n O m clusters were correctly reproduced by us, 17 better ones were found, and 197 clusters were studied for the first time to our best knowledge (see table 1 in SI). Fig.…”

supporting

confidence: 74%

“…315 cluster compositions). We note that the earlier investigations of Si n O m were either done for relatively small clusters (n ≤ 7) 6,26,28,30,31 or focused on stoichiometric compounds (SiO) n or (SiO 2 ) n . 4,10,27,32,33 Even for these compounds it is often seen that newer papers report lowerenergy structures than the older ones.…”

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confidence: 99%

Method for Simultaneous Prediction of Atomic Structure and Stability of Nanoclusters in a Wide Area of Compositions

Lepeshkin

Baturin

Uspenskii

et al. 2018

J. Phys. Chem. Lett.

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We present a universal method for the largescale prediction of the atomic structure of clusters. Our algorithm performs the joint evolutionary search for all clusters in a given area of the compositional space and takes advantage of structural similarities frequently observed in clusters of close compositions. The resulting speedup is up to 50 times compared to current methods. This enables the first-principles studies of multi-component clusters with full coverage of a wide range of compositions. As an example, we report an unprecedented firstprinciples global optimization of 315 Si n O m clusters with n ≤ 15 and m ≤ 20. The obtained map of Si-O cluster stability shows the existence of both expected (SiO 2 ) n and unexpected (e.g. Si 4 O 18 ) stable (magic) clusters, which can be important for miscellaneous applications.Graphical TOC Entry 1 arXiv:1812.06568v1 [cond-mat.mtrl-sci] 17 Dec 2018The unique properties of nanoparticles are extensively used in optoelectronics, photovoltaics, photocatalysis, biomedicine, etc. These properties are closely linked to the atomic structure of particles, what is more explicit in the small particles and nanoclusters. 1,2 Despite the importance of knowing the structure, its experimental determination remains very difficult. 3 For this reason the main body of structural information on clusters is obtained via first-principles calculations 4 which were mostly done either for monoatomic clusters or for binary clusters of stoichiometric composition corresponding to the bulk compounds, while clusters of general composition were studied only in few publications. 5,6 Such an accent in ab initio research ignores the fact that the chemistry of clusters is much richer than that of solids because of a large share of surface atoms. Multi-component clusters often have stable compositions, which are far from chemical compounds presented in the bulk x-T phase diagram. This is of interest not only for basic chemistry of clusters. It significantly increases the scope of candidate nanomaterials for practical applications such as: the development of efficient and affordable catalysts 7,8 and magnets, 9 the investigation of complex processes of nucleation and particle growth, 10-12 etc.The bottle-neck of first-principles activity in cluster studies is the computational cost of atomic structure determination, which is a global optimization of the total energy among all possible atomic configurations. There are several methods of structure prediction (basin and minima hopping, 13,14 simulated annealing, 15 evolutionary algorithm, 16 etc.), however they all involve thousands of local optimizations (relaxations) even for finding a structure of one cluster. In the applications mentioned above, the computation of atomic structure and the screening of stability and properties are required in wide regions including hundreds of cluster compositions, therefore such firstprinciples investigations turn out extremely exhausting. To reduce the computational cost, the global optimization is frequently performed ...

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“…reproduce experimental values of properties of neutral and ionic Si n O m species and also the results of higher-level calculations. [1,3,[8][9][10] Møller-Plesset second-order perturbation theory (MP2) has been used to perform intrinsic reaction coordinate (ICR) and energy barrier calculations of several Si n O m clusters reactions, obtaining results in reasonable agreement with coupled cluster methods. [11] For the PES calculations performed in this work, scans at the MP2/6-31G(d) level of theory (including all electrons) were carried out at specific locations of the PES, to obtain more accurate energy values of possible transition states and barriers.…”

Section: Original Articlesmentioning

confidence: 99%

Charge‐transfer processes in the assembly of Si_nO_m neutral clusters

Jadraque

Martı́n

2011

J Comput Chem

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The chemical bond formation in oxygen-rich Si(n)O(m) clusters was investigated by sampling the potential energy surface of the model systems SiO + SiO(2) → Si(2)O(3) and (SiO)(2) + SiO(2) → Si(3)O(4) along a two-dimensional reaction coordinate, by density functional theory calculations. Evidence for crossing between the weakly bound neutral-neutral (SiO)(n) + SiO(2) and the highly attractive ion-pair (SiO)(n)(+) + SiO(2)(-) surfaces was found. Analysis of frontier molecular orbitals and charge distribution showed that surface crossing involves transfer of valence electron charge from (SiO)(2) to SiO(2). The sum of the natural atomic charges over the (SiO)(n) and (SiO(2)) groups of the Si(n)O(m) cluster products, gave a net positive charge on the (SiO)(n) "core" and a net negative charge on the (SiO(2)) groups. This is interpreted as the "ion-pair memory" left on the Si(n)O(m) products by the charge-transfer mechanism and may provide a way to assess the role of charge-transfer processes in the assembly of larger Si(n)O(m) neutral clusters.

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Theoretical prediction of atomic and electronic structure of neutral Si6Om (m=1–11) clusters

Cited by 10 publications

References 49 publications

Vibrational spectra and structures of neutral Si₆X clusters (X = Be, B, C, N, O)

Vibrational spectra and structures of neutral Si₆X clusters (X = Be, B, C, N, O)

Method for Simultaneous Prediction of Atomic Structure and Stability of Nanoclusters in a Wide Area of Compositions

Charge‐transfer processes in the assembly of Si_nO_m neutral clusters

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Theoretical prediction of atomic and electronic structure of neutral Si6Om (m=1–11) clusters

Cited by 10 publications

References 49 publications

Vibrational spectra and structures of neutral Si6X clusters (X = Be, B, C, N, O)

Vibrational spectra and structures of neutral Si6X clusters (X = Be, B, C, N, O)

Method for Simultaneous Prediction of Atomic Structure and Stability of Nanoclusters in a Wide Area of Compositions

Charge‐transfer processes in the assembly of SinOm neutral clusters

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Product

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Vibrational spectra and structures of neutral Si₆X clusters (X = Be, B, C, N, O)

Vibrational spectra and structures of neutral Si₆X clusters (X = Be, B, C, N, O)

Charge‐transfer processes in the assembly of Si_nO_m neutral clusters