O + C2H4 potential energy surface: excited states and biradicals at the multireference level

摘要

The focus of this study is to understand the multiconfigurational nature of the biradical species involved in the early reaction paths of the oxygen plus ethylene PES. In previous work (J Phys Chem A 113, 12663, 2009), the lowest-lying O(3P) + C2H4 PES was extensively explored at the MCSCF, MRMP2, and MR-AQCC levels of theory. In the current work, ground and excited, triplet- and singlet-state reaction paths for the initial addition of oxygen to ethylene were found at the MCSCF and MRMP2 levels along with five singlet pathways near the ·CH2CH2O· biradical at the MCSCF, MRMP2, and CR-CC(2,3) levels. One of these five paths can lead to the CH2CO + H2 products from CH3CHO rather than from the ·CH2CH2O· biradical, and this pathway was investigated with a variety of CAS sizes. To provide further comparison between the MRMP2 and CR-CC(2,3) levels, MR-AQCC single-point energies and optimizations were performed for select geometries. After the initial exploration of this region of the surface, the lowest singlet–triplet surface crossings were explicitly determined at the MCSCF level. Additional MRMP2 calculations were performed to demonstrate the limitations of single-state perturbation theory in this biradical region of the PES, and SO-MCQDPT2 single-point energies using SA MCSCF were calculated on a grid of geometries around the primary surface crossing. In particular, these calculations were examined to determine a proper active space and a physically reasonable number of electronic states. The results of this examination show that at least four states must be considered to represent this very complex region of the PES.