The MRCI studies of low-lying electronic states of Al3 and

Czernek, Jiřı́; Živný, Oldřich

doi:10.1016/j.cplett.2011.07.004

Cited by 9 publications

(3 citation statements)

References 26 publications

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“…As can be seen in Tables and , the bond lengths of Al 2 and Al 3 – calculated by CCSD(T)/def2-QZVPP are in excellent agreement with the experimental values. In addition, the bond length of Al 3 optimized by CCSD(T)/def2-QZVPP (2.523 Å) is very similar to that (2.534 Å) of MRCI/aug-cc-pVQZ . All the results suggest that the values calculated by CCSD(T)/def2-QZVPP can be considered as reference values for further comparisons.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2013

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We report the results of a benchmarking study on hybrid, hybrid-meta, long-range-corrected, meta-generalized gradient approximation (meta-GGA), and GGA density functional theory (DFT) methods for aluminum (Al) clusters. A range of DFT functionals, such as B3LYP, B1B95, PBE0, mPW1PW91, M06, M06-2X, ωB97X, ωB97XD, TPSSh, BLYP, PBE, mPWPW91, M06-L, and TPSS, have been used to optimize the molecular structures and calculate the vibrational frequencies and four energetic parameters for neutral and anionic Al(n) (n = 2-10) clusters. The performances of these functionals are assessed systematically by calculating the vertical ionization energy for neutral Al clusters and the vertical electron detachment energy for anionic Al clusters, along with the cohesive energy and dissociation energy. The results are compared with the available experimental and high-level ab initio calculated results. The calculated results showed that the PBE0 and mPW1PW91 functionals generally provide better results than the other functionals studied. TPSS can be a good choice for the calculations of very large Al clusters. On the other hand, the B3LYP, BLYP, and M06-L functionals are in poor agreement with the available experimental and theoretical results. The calculated results suggest that the hybrid DFT functionals like B3LYP do not always provide better performance than GGA functionals.

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Section: Resultsmentioning

confidence: 99%

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

et al. 2013

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“…Hydrated Al trimers are small enough for benchmarking purposes. Al 3 has been the subject of intense experimental and theoretical work. − Al 13 is a very stable cluster with nearly icosahedral symmetry, ,− perhaps the first representative of larger systems or Al crystals.…”

Section: Introductionmentioning

confidence: 99%

How Fast Do Microhydrated Al Clusters React: A Theoretical Study

Álvarez‐Barcia

Flores

2011

J. Phys. Chem. C

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The dynamics of the first step of the reaction of small Al m clusters m = {3,13} with up to four water molecules has been studied. The first stage in the reaction, which may ultimately result in the production of H2, is the generation of a HAl m OH·(H2O) n−1 species, which can take place through transition states of the relay type, in which the water molecules may play different catalytic roles; namely, they can be involved directly in a Grotthuss-like mechanism by forming a relay bridge, or they may lower the saddle point energy by interacting with the molecules of the relay bridge. Rate coefficients have been computed with the inclusion of tunneling effects. The results indicate that the optimal configuration (the one giving the highest values of the rate coefficient for 50 K < T < 500 K) in the case of the Al3·(H2O) n system involves three water molecules in the relay bridge. In the case of the Al13 cluster, the two-water system is the most efficient. It is remarkable that Al3 delivers much higher rates than Al13 or a single Al atom. It is argued that Al13 and Al have, somehow, a similar behavior from the point of view of the rates, the Gibbs activation energies, and the tunneling transmission coefficients, which gives some dynamically based support to viewing the Al13 cluster as a kind of “superatom”.

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“…Metal clusters comprising a few to a few hundred atoms allow for chemistry distinct from the bulk scale. − For instance, clusters containing certain “magic” numbers of electrons display increased stability, rationalized, in part, through the jellium model, treating valence electrons as distributed about a homogeneously positive core. , Notably, several aluminum clusters display increased stability to reaction with ground-state O 2 , − providing a potential means to exploit the large exothermicity of the oxidation reaction while avoiding the increased vaporization energy of the bulk. Numerous experimental − and theoretical studies − have investigated aluminum anion clusters, often focusing on Al 13 – , which is “doubly magic” in having a closed jellium shell and a highly symmetric ground-state structure. Distributions of Al n – etch down to leave primarily Al 13 – in the presence of O 2 , indicating that Al 13 – is more stable to O 2 than other cluster sizes. , Some reports have stated that Al 13 – is unreactive, while others have specified an upper limit to the rate constant on the order of 10 –13 cm 3 s –1 …”

Section: Introductionmentioning

confidence: 99%

Thermal Kinetics of Al_n^– + O₂ (n = 2–30): Measurable Reactivity of Al₁₃^–

et al. 2019

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Mass-selected aluminum anion clusters, Al n − , were reacted with O 2 . Rate constants (300 K) for 2 < n < 30 and product branching fractions for 2 < n < 17 are reported. Reactivity is strongly anticorrelated to Al n − electron binding energy (EBE). Al 13 − reacts more slowly than predicted by EBE but notably is not inert, reacting at a measurable 0.05% efficiency (2.5 ± 1.5 × 10 −13 cm 3 s −1 ). Al 6 − is also an outlier, reacting more slowly than expected after accounting for other factors, suggesting that high symmetry increases stability. Implications of observed Al 13 − reactivity, contributions of both electronic shell-closing and geometric homogeneity to Al n − resistance to O 2 etching, and future directions to more fully unravel the reaction mechanisms are discussed.

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The MRCI studies of low-lying electronic states of Al3 and

Cited by 9 publications

References 26 publications

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

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

How Fast Do Microhydrated Al Clusters React: A Theoretical Study

Thermal Kinetics of Al_n^– + O₂ (n = 2–30): Measurable Reactivity of Al₁₃^–

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The MRCI studies of low-lying electronic states of Al3 and

Cited by 9 publications

References 26 publications

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

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

How Fast Do Microhydrated Al Clusters React: A Theoretical Study

Thermal Kinetics of Aln– + O2 (n = 2–30): Measurable Reactivity of Al13–

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

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

Thermal Kinetics of Al_n^– + O₂ (n = 2–30): Measurable Reactivity of Al₁₃^–