Investigation of the reactions of small neutral iron oxide clusters with methanol

Reactions of neutral iron oxide clusters (FemOn, m=1–2, n=0–5) with methanol (CH3OH) in a fast flow reactor are investigated by time of flight mass spectrometry. Detection of the neutral iron oxide cluster distribution and reaction intermediates and products is accomplished through single photon ionization by a 118 nm (10.5 eV) VUV laser. Partially deuterated methanol (CD3OH) is employed to distinguish reaction products and reaction mechanisms. Three major reactions are identified experimentally: CH3OH association with FeO; methanol dehydrogenation on FeO1,2 and Fe2O2–5; and (CH2O)Fe formation. Density functional theory calculations are carried out to identify reaction products, and to explore the geometric and electronic structures of the iron oxide clusters, reaction intermediates, and transition states, and to evaluate reaction pathways. Neutral formaldehyde is calculated to be formed on FeO1,2 and Fe2O2–5 clusters. Hydrogen transfer from methanol to iron oxide clusters occurs first from the O–H moiety...