Theoretical study of the CO2–O2 van der Waals complex: potential energy surface and applications

A four-dimensional-potential energy surface (4D-PES) of the atmospherically relevant carbon dioxide–oxygen molecule (CO2–O2) van der Waals complex is mapped using the ab initio explicitly correlated coupled cluster method with single, double, and perturbative triple excitations (UCCSD(T)-F12b), and extrapolation to the complete basis set (CBS) limit using the cc-pVTZ-F12/cc-pVQZ-F12 bases and the l−3 formula. An analytic representation of the 4D-PES was fitted using the method of interpolating moving least squares (IMLS). These calculations predict that the most stable configuration of CO2–O2 complex corresponds to a planar slipped-parallel structure with a binding energy of V ∼ −243 cm−1. Another isomer is found on the PES, corresponding to a non-planar cross-shaped structure, with V ∼ −218 cm−1. The transition structure connecting the two minima is found at V ∼ −211 cm−1. We also performed comparisons with some CO2–X van der Waals complexes. Moreover, we provide a SAPT analysis of this molecular system. Then, we discuss the complexation induced shifts of CO2 and O2. Afterwards, this new 4D-PES is employed to compute the second virial coefficient including temperature dependence. A comparison between quantities obtained in our calculations and those from experiments found close agreement attesting to the high quality of the PES and to the importance of considering a full description of the anisotropic potential for the derivation of thermophysical properties of CO2–O2 mixtures.