Vibrationally resolved photoelectron spectroscopy of the first row transition metal and C3 clusters: MC3− (M=Sc, V, Cr, Mn, Fe, Co, and Ni)

Abstract

We report photoelectron spectra of the MC 3 Ϫ clusters for MϭSc, V, Cr, Mn, Fe, Co, and Ni at two photon energies, 355 and 266 nm. Vibrational structure is resolved for the ground and excited state detachment transitions for all the clusters except for CoC 3 Ϫ and NiC 3 Ϫ. Electron affinity ͑EA͒ and vibrational frequencies for the MC 3 clusters are obtained. Complicated low-lying excited state features are observed for all the species. We find that the trend of the EA across the 3d series for the MC 3 clusters is similar to that of the MC 2 species. The vibrational frequency is found to increase from ScC 3 to TiC 3 and then decreases monotonically to the right of the 3d series. Preliminary density functional theory calculations are performed on all the MC 3 and MC 3 Ϫ clusters at several initial geometries and spin multiplicities. We find that the ground states of all the MC 3 and MC 3 Ϫ species have C 2v ring structures. The calculated M-C stretching frequency for all the MC 3 species is in good agreement with the experimental measurement, lending credence to the obtained C 2v structure.

Characterization of Magnetic Series of Iron–Carbon Clusters FenC0,±1 (n ≤ 13)

“…The theoretical characterization of the interaction among a few carbon and iron atoms has been approached in several manners. − One of them deals with a single iron atom interacting with a small amount of carbon atoms. Reports on the dimer FeC − and FeC n ( n = 2–10) − clusters are a few examples of this category. Another point of view treats with interactions among a few iron and carbon atoms that are structurally mixed.…”

Ground and Low-Lying Excited States of NbC3–/0 Clusters: Assignment of the Anion Photoelectron Spectra from Multiconfigurational Calculations

“…Investigations on transition metal carbide clusters have been performed by using both experimental and theoretical methods. Photoelectron spectroscopy has been known as a popular experimental technique which can be employed to probe the relative energetic positions of low-lying electronic states. − In the literature, a large number of photoelectron spectra of transition metal carbide clusters have been reported. − Also, quantum chemical calculations have been proven to be vital for acquiring the geometric and electronic structures of these kind of clusters. ,− It is well-known that they show strong electron correlation and multireference wave effects, which implies the need for highly accurate computational methods such as coupled-cluster theory (CCSD­(T)), complete active space second-order perturbation theory (CASPT2), and multireference configuration interaction (MRCI). ,,,− In many cases, the computational results turned out to be essential for assigning the anion photoelectron spectra. − …”

First-principle study of structural, electronic and magnetic properties of (FeC)n (n = 1–8) and (FeC)8TM (TM = V, Cr, Mn and Co) clusters

“…Recently, Wang et al . 31 reported photoelectron spectra of FeC 3 − cluster, and found that the ground states of FeC 3 and FeC 3 − clusters have C 2v ring structures. Using gas phase ion chromatography, Helden et al .…”