Acetone Dimer Hydrogenation under Vacuum Ultraviolet: An Intracluster Trimolecular Dissociation Mechanism.

Abstract

Hydrogenation of organic chemicals is one of the most frequent things that people take for granted in mass spectroscopy; however, it could provide important information on spontaneous or stimulated hydrogen transfer in initiating chemical reactions and in determining the product selectivity and conversion efficiency. Here, we present a study of hydrogenation of acetone via vacuum ultraviolet laser ionization mass spectrometry (VUV-LIMS) and density functional theory (DFT) calculations. It is interestingly found that acetone dimer readily captures a hydrogen to form (C3H6O)2H+ in the presence of alcohols, shedding light on the intracluster hydrogen atom transfer via a trimolecular mechanism. This is well consistent with the DFT calculation results of energetics and reaction kinetics. It is worth noting that, although the hydrogen bond interaction of O-H···O is stronger than that of C-H···O, the hydrogen atom transfer (HAT) tends to proceed from the methyl group of the alcohols to acetone. We fully demonstrate the intracluster HAT reactivity of such a simple system and provide new insights into hydrogen bond interactions and molecular cluster chemistry.