New Theoretical Infrared Line List for the Methyl Radical with Accurate Vibrational Band Origins from High-Level Ab Initio Calculations.

In the present work, high-level ab initio calculations were carried out for the ground electronic state of the methyl radical (CH 3 ). Dunning's augmented correlation-consistent orbital basis sets were employed up to the quintuple-ζ valence quality with the core-valence electron correlation [aug-cc-pCV5Z] combined with the single- and double-excitation unrestricted coupled-cluster approach with a perturbative treatment of triple excitations [RHF-UCCSD(T)]. The explicitly correlated version of the coupled-cluster approach [RHF-UCCSD(T)-F12x{x = a, b}] was additionally applied with the core-valence cc-pCVQZ-F12 basis set in order to study convergence with respect to the basis set size. The contributions beyond the coupled-cluster level of the theory like Douglas-Kroll-Hess scalar relativistic Hamiltonian, diabatic Born-Oppenheimer corrections, and high-order electronic correlations have been included into the ab initio potential energy surfaces (PESs). It is shown that the theoretical band origins of CH 3 converge gradually to the experimental values when applying the ab initio PESs using the aug-cc-pCVXZ [X = T, Q, and 5] basis sets. For the first time, all available experimental band origins of the gaseous CH 3 are reproduced within an accuracy of 0.2 cm -1 using a newly developed PES extrapolated to the complete basis set limit [CBS(TQ5Z)]. The reached accuracy is one order of magnitude better than that of the best available calculations. A new theoretical infrared line list was generated for astrophysical applications using an ab initio dipole moment surface computed at the RHF-UCCSD(T)/aug-cc-pCVQZ level of the theory. The manifestation of a large-amplitude motion in CH 3 is also discussed.