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 Mn 2 unit. Mn 2 Si 12 and [Mn 2 Si 13 ] + are both axially symmetric, allowing for a clean separation of the vibrational modes into parallel (a 1 ) and perpendicular (e 1 ) 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 [Mn 2 Si 13 ] + , where the antiprismatic core is capped on both hexagonal faces, a relatively simple spectrum emerges that reflects a pseudo-D 6 d geometry. In cases where the cluster is more polar, either because there is no capping atom in the lower face (Mn 2 Si 12 ) or the capping atom is present but displaced off the principal axis (Mn 2 Si 13 ), the spectra include additional features derived from vibrational modes that are forbidden in the parent antiprism.

Anion photoelectron spectroscopy and density functional theory study of TM2Sin− (TM = V, Cr; n = 14–20) clusters

“…12 Hexagonal antiprisms have already been found for example for V 2 Si 12 − , 12 Cr 2 Si 13 , Cr 3 Si 12 0/− 46 and Mn 2 Si 12 , 13 . 65…”

“…Overall the TM-TM bonds are much larger than the corresponding gas phase dimer bond lengths (V 2 : 1.77 Å; 67 , by removing the upper seven-membered ring of Si atoms). It can be generated from a fullerene-like TM@Si 14 structure 30,65 by removing one of the Si atoms and replacing another one by a TM atom. In the case of V 2 Si 18 À the Si atom and the TM atom on top of the cage are exchanged.…”

Small chromium-doped silicon clusters CrSin: structures, IR spectra, charge effect, magnetism and chirality

“…. [31][32][33][34][35][36][37][38][39][40][41] and pure cationic (n = 6-11, 13-15, 18) 42 and neutral Si n (n = 6-10, 15) 43,44 clusters.…”

“…Previous joint experimental and computational studies using infrared multiple photon dissociation (IR-MPD) spectroscopy, far-infrared-vacuum-ultraviolet two color ionization spectroscopy, and DFT calculations have successfully assigned the geometrical structures of different metal clusters such as the Au clusters, 27–29 the recently discovered NbAl 8 H 8 + cluster, 30 cationic and neutral metal-doped silicon clusters M@Si n with Cu, V, Mn, Co, Ag, Au, Nb… 31–41 and pure cationic ( n = 6–11, 13–15, 18) 42 and neutral Si n ( n = 6–10, 15) 43,44 clusters.…”

Virtual Issue on Experiment–Theory Synergies in the Study of Metal and Metal-Containing Clusters

“…These techniques are also applied to metal-containing mixed clusters with synergistic results. Beautiful symmetries and particular electronic stabilities can be gleaned from interpretation of experimental spectra (e.g., anion PE spectra, vibrational spectra) informed by theory, such as in the case of metal-doped silicon clusters − studied by Dai et al, Khanna et al, and Yang et al, respectively. Other mixed clusters, particularly those with trans-periodic combinations, can inform the design of advanced materials.…”