Electronic structure, bonding and stability of fumarate, maleate, and succinate dianions from X-ray spectroscopy

Abstract

The electronic structure of the fumarate, maleate, and succinate dianions in the context of their stability is determined in a joint experimental and computational study with X-ray absorption spectroscopy and resonant inelastic X-ray scattering at the O K-edge. The study reveals differences in the electronic states and molecular orbitals of the three molecules. In particular, maleate has a non-degenerate oxygen core-orbital with an energy difference of approximately 0.15 eV, visible in a two peak structure in XAS. Polarization-dependent RIXS provides information on the orientation of the occupied valence molecular orbitals with respect to the carboxylate group plane and shows a gradually increasing energy gap between the HOMO and excited π* LUMO from fumarate to maleate to succinate. We also demonstrate the energy excitation dependence of the RIXS spectra of maleate, with the total inelastic RIXS profile shifting towards higher energy loss as the detuning is increased from negative to positive values. Our findings show that maleate is less stable than fumarate and succinate due to the presence of electronic density on its HOMO orbital on the CC bond between carboxylate groups, which can lead to weaker bonding of maleate with molecules or ions.