Evolution of vibrational spectra in the manganese–silicon clusters Mn2Sin, n = 10, 12, and 13, and cationic [Mn2Si13]+

Journal article

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.

Authors: Khanna, V; Singh, R; Claes, P; Nguyen, MT; Fielicke, A

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: The Journal of Physical Chemistry A
• Volume: 126
• Issue: 10
• Pages: 1617-1626
• Place of publication: United States
• Publication date: 2022-03-03
• Acceptance date: 2022-02-17
• DOI: 10.1021/acs.jpca.1c10027
• EISSN: 1520-5215
• ISSN: 1089-5639
• Pmid: 35238570
• Language: English
• Keywords: Cluster chemistry; Transition metals; FFR; Silicon; Chemical structure; Group theory