The effects of water microsolvation on the C2O4− ↔ CO2·CO2− core switching reaction: Perspective from exploration of pathways on the potential energy surfaces of small [(CO2)2(H2O)n]− (n = 1 and 2) clusters

Abstract

Water microsolvation effects on the C2O4−↔CO2·CO2− anion core switching reaction in the small [(CO2)2(H2O)n]− (n=1 and 2) clusters have been computationally studied. All low-energy rearrangement pathways have been explored using global reaction route mapping (GRRM) techniques. Both the C2O4− dimer anion core and CO2·CO2− monomer anion core have various hydration structures. The former is stable in [(CO2)2(H2O)1]− while the latter becomes stable in [(CO2)2(H2O)2]−. It was found that the energy levels of the transition states significantly depend on the detailed hydration structures. We also performed Born-Oppenheimer molecular dynamics calculations to simulate photoelectron spectra of the [(CO2)2(H2O)n]− clusters.