Photodissociation mechanisms of the CO2(2+) dication studied using multi-state multiconfiguration second-order...

Employing the multi-state multiconfiguration second-order perturbation theory (MS-CASPT2) and complete active space self-consistent field (CASSCF) methods, the geometries, relative energies (T(v)') to the ground state (X(3)Σg(-)), adiabatic excited energies, and photodissociation mechanisms and corresponding kinetic energy releases for the lower-lying 14 electronic states of the CO2 (2+) ion are studied. The T(v)' values are calculated at the experimental geometry of the ground state CO2 molecule using MS-CASPT2 method and highly close to the latest threshold photoelectrons coincidence and time-of-flight photoelectron photoelectron coincidence spectrum observations. The O-loss dissociation potential energy curves (PECs) for these 14 states are drawn using MS-CASPT2 partial optimization method at C(∞v) symmetry with one C-O bond length ranging from 1.05 to 8.0 Å. Those 14 states are confirmed to be correlated to the lowest four dissociation limits [CO(+)(X(2)Σ(+)) + O(+)((4)S(u)), CO(+)(A(2)Π) + O(+)((4)S(u)), CO(+)(X(2)Σ(+)) + O(+)((2)D(u)), and CO(+)(X(2)Σ(+)) + O(+)((2)P(u))] by analyzing Coulomb interaction energies, charges, spin densities, and bond lengths for the geometries at the C-O bond length of 8.0 Å. On the basis of these 14 MS-CASPT2 PECs, several state/state pairs are selected to optimize the minimum energy crossing points (MECPs) at the CASSCF level. And then the CASSCF spin-orbit couplings and CASPT2 state/state energies are calculated at these located MECPs. Based on all of the computational results, the photodissociation mechanisms of CO2(2+) are proposed. The relationships between the present theoretical studies and the previous experiments are discussed.