Ionization potentials for the H₂CO trimer

In this work, a computational study on the ionization potentials (IPs) of the formaldehyde trimer, (H₂CO)₃, is presented. Twelve lowest-lying vertical IPs were determined through the use of the coupled-cluster level of theory using correlation consistent basis sets with extrapolation to the complete basis set limit and consideration of core electron correlation effects. Specifically, the equation-of-motion ionization potential coupled-cluster with single and double excitations method with the aug-cc-pVnZ and aug-cc-pCVnZ (n = D and T) basis sets was used. The Feller-Peterson-Dixon (FPD) composite approach was employed to provide accurate IPs, and eight conformations of (H₂CO)₃ were considered. The FPD IPs determined for (H₂CO)₃ were found to be systematically lower than those computed for the dimer and monomer of H₂CO in the pattern IP_(monomer) > IP_(dimer) > IP_(trimer) for a given IP. In addition, the IPs calculated when considering only the more stable conformation (C₀) are in good agreement with those obtained using the eight conformations of the H₂CO trimer, and thus, the actual conformation played only a minor role in determining such properties in the present case. By providing first accurate IP results for the H₂CO trimer, we hope to motivate future experimental and computational investigations (e.g., studies involving photoionization) that rely on such quantities.