Carbon dioxide interacting with rare gases: Insights from high-level ab initio calculations of polarizability and hyperpolarizability effects

- CO2⋯Rg, Rg = He, Ne, Ar, Kr and Xe complexes.
- High-level ab initio calculations.
- Purpose-oriented Gaussian basis sets are used on CO2 and Rg.
- Interaction-induced dipole moment.
- Interaction-induced dipole (hyper)polarizability.

We have obtained a quantitative, synthetic picture of the interaction-induced (hyper)polarizability in the sequence of the weakly bound complexes CO2⋯Rg, Rg = He, Ne, Ar, Kr, Xe. The properties are calculated from finite-field Møller-Plesset perturbation theory and coupled cluster calculations. We rely on flexible, prepared purpose-oriented atom- and molecule-specific basis set of Gaussian-type functions. We obtained interaction-induced electric properties for both the most stable T-shaped configuration and the less stable L-shaped one. Our interaction-induced first and second hyperpolarizabilities for the most stable (T-shaped) configurations, at the second order Møller-Plesset perturbation theory level are β¯int/e3a03Eh-2 (CO2⋯Rg) = 1.14 (He), 2.02 (Ne), 2.50 (Ar), 0.50 (Kr) and −5.32 (Xe). For the second hyperpolarizability at the same level of theory γ¯int/e4a04Eh-3 (CO2⋯Rg) = −11.66 (He), −25.88 (Ne), −108.16 (Ar), −206.75 (Kr) and −460.42 (Xe). In the vicinity of the equilibrium configuration, with the Rg atom displaced on the x axis for T-shaped configuration, the first hyperpolarizability changes as dβ¯dRee3a02Eh-2 (CO2⋯Rg) = −1.07 (He), −1.86 (Ne), −0.71 (Ar), 2.65 (Kr) and 9.96 (Xe). For the second hyperpolarizability dγ‾dRee4a03Eh-3 (CO2⋯Rg) = 7.94 (He), 20.34 (Ne), 65.00 (Ar), 118.48 (Kr) and 239.84 (Xe).