Dataset Information

Evolution of Vibrational Spectra in the Manganese-Silicon Clusters Mn₂Si_n, n = 10, 12, and 13, and Cationic [Mn₂Si₁₃].

ABSTRACT: A comparison of DFT-computed and measured infrared spectra reveals the ground state structures of a series of gas-phase silicon clusters containing a common Mn₂ unit. Mn₂Si₁₂ and [Mn₂Si₁₃]⁺ are both axially symmetric, allowing for a clean separation of the vibrational modes into parallel (a₁) and perpendicular (e₁) components. Information about the Mn-Mn and Mn-Si bonding can be extracted by tracing the evolution of these modes as the cluster increases in size. In [Mn₂Si₁₃]⁺, where the antiprismatic core is capped on both hexagonal faces, a relatively simple spectrum emerges that reflects a pseudo-D_6d geometry. In cases where the cluster is more polar, either because there is no capping atom in the lower face (Mn₂Si₁₂) or the capping atom is present but displaced off the principal axis (Mn₂Si₁₃), the spectra include additional features derived from vibrational modes that are forbidden in the parent antiprism.

SUBMITTER: Khanna V

PROVIDER: S-EPMC9084549 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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Publications

Evolution of Vibrational Spectra in the Manganese-Silicon Clusters Mn2Sin, n = 10, 12, and 13, and Cationic [Mn2Si13].

Khanna Vaibhav V Singh Roshan R Claes Pieterjan P Nguyen Minh Tho MT Fielicke André A Janssens Ewald E Lievens Peter P McGrady John E JE

The journal of physical chemistry. A 20220303 10

A comparison of DFT-computed and measured infrared spectra reveals the ground state structures of a series of gas-phase silicon clusters containing a common Mn2 unit. Mn2Si12 and [Mn2Si13]+ are both axially symmetric, allowing for a clean separation of the vibrational modes into parallel (a1) and perpendicular (e1) components. Information about the Mn-Mn and Mn-Si bonding can be extracted by tracing the evolu ...[more]

PMID: 35238570

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Project description:High-accuracy quantum chemical calculations were carried out to study the mechanisms and catalytic abilities of various mixed silicon species Si2M with M = H, Li, Na, Cu, and Ag toward the first step of methanol activation reaction. Standard heats of formation of these small triatomic Si clusters were determined. Potential-energy profiles were constructed using the coupled-cluster theory with extrapolation to complete basis set CCSD(T)/CBS, and CCSD(T)/aug-cc-pVTZ-PP for Si2Cu and Si2Ag. The most stable complexes generated by the interaction of methanol with the mixed clusters Si2M possess low-spin states and mainly stem from an M-O connection in preference to Si-O interaction, except for the Si2H case. In two competitive pathways including O-H and C-H bond breakings, the cleavage of the O-H bond in the presence of all clusters studied becomes predominant. Of the mixed clusters Si2M considered, the dissociation pathways of both O-H and C-H bonds with Si2Li turns out to have the lowest energy barriers. The most remarkable finding is the absence of the overall energy barrier for the O-H cleavage with the assistance of Si2Li. The breaking of O-H and C-H bonds with the assistance of Si2H, Si2Li, and Si2Na is kinetically preferred with respect to the Si2Cu and Si2Ag cases, apart from the case of Si2Na for O-H cleavage. In comparison with other transition-metal clusters with the same size, such as Cu3, Pt3, and PtAu2, the energy barriers for the O-H bond activation in the presence of small Si species, especially Si2H and Si2Li, are found to be lower. Consequently, these small mixed silicon clusters can be regarded as promising alternatives for the expensive metal-based catalysts currently used for methanol activation particularly and other dehydrogenation processes of organic compounds. The present study also suggests a further extensive search for other doped silicon clusters as efficient and more realistic gas-phase catalysts for important dehydrogenation processes in such a way that they can be experimentally prepared and implemented.

Dataset Information

Evolution of Vibrational Spectra in the Manganese-Silicon Clusters Mn₂Si_n, n = 10, 12, and 13, and Cationic [Mn₂Si₁₃].

Publications

Evolution of Vibrational Spectra in the Manganese-Silicon Clusters Mn<sub>2</sub>Si<sub><i>n</i></sub>, <i>n</i> = 10, 12, and 13, and Cationic [Mn<sub>2</sub>Si<sub>13</sub>].

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