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5. Vibrational Spectroscopy and Structural Analysis of V⁺(C₂H₆)_n Clusters (n = 1–4)

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   Marcum, Jesse C; Metz, Ricardo B (June 2023, The Journal of Physical Chemistry A)

   The vibrational structure and binding motifs of vanadium cation-ethane clusters, V(+)(C2H6)n, for n = 1 – 4 are probed using infrared photodissociation spectroscopy in the C-H stretching region (2550 – 3100 cm-1). Comparison of spectra to scaled harmonic frequency spectra obtained using density functional theory suggest that ethane exhibits two primary binding motifs when interacting with the vanadium cation, an end-on 𝜂2 configuration and a side-on configuration. The lower-energy side-on configuration predominates in smaller clusters, but the end-on configuration becomes important for larger clusters as it helps to maintain a roughly square planar geometry about the central vanadium. Proximate C-H bonds exhibit elongation and large red-shifts when compared to bare ethane, particularly in the case of the side-on isomer, which are underestimated by scaled harmonic frequency calculations, demonstrating initial effects of C-H bond activation. 

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