Probing the ionization potentials of the formaldehyde dimer

In this work, we present a computational investigation on the ionization potentials (IPs) of the formaldehyde dimer, (H₂CO)₂. Twelve lowest lying IPs (corresponding to the entire valence orbitals) for both C_2h and C_s symmetry conformers have been computed at the coupled cluster level of theory using large 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 (EOMIP-CCSD) excitations method with the aug-cc-pVXZ and aug-cc-pCVXZ (X = T, Q, and 5) basis sets combined with the Feller-Peterson-Dixon approach was employed, as well as CCSD with perturbative triples [CCSD(T)] with the aug-cc-pVTZ basis sets. In general, excellent agreement was observed from the comparison between the results obtained through the use of these approaches. In addition, the IPs for the formaldehyde monomer were also obtained using such methodologies and the results compared with existing experimental data; excellent agreement was also observed in this case. To the best of our knowledge, this work represents the first of its kind to determine the IPs for all these systems using a high level theory approach and is presented to motivate experimental investigations, e.g., studies involving photoionization, particularly for the formaldehyde dimer. The equilibrium binding energy of the C_2h dimer is calculated in this work at the CCSD(T)/aug-cc-pVTZ level of theory to be -4.71 kcal/mol. At this same level of theory, the equilibrium isomerization energy between C_2h and C_s conformers is 0.76 kcal/mol (C_s conformer being more stable).