Rovibrational Line Lists of Triplet and Singlet Methylene.

The methylene molecule (CH 2 ) is a short-lived radical with lacking data on its spectral line intensities. Although the lifetime of CH 2 is extremely short under Earth's conditions, it exists in a free form in interstellar media. CH 2 is an important intermediate species in chemical reactions associated with the formation and destruction of complex hydrocarbons. We present the first rovibrational line lists of CH 2 in its ground triplet and first excited singlet electronic state. To this end, our previously developed accurate ab initio potential energy surface (PES) was used for the ground electronic triplet state [Egorov et al . J. Comp. Chem. 2024. V. 45. (2). P. 83] while a new PES for the singlet state was constructed in this work using the single-reference coupled cluster approach [CCSD(T)] combined with the extrapolation to the complete basis set (CBS) limit based on the correlation-consistent orbital basis sets with the core-valence electron correlation effects [aug-cc-pCVXZ, X = T, Q, 5, and 6]. In addition, the contributions to the correlation energy from highly excited Slater determinants [CC( n ), n = 3-5] were included as well as the scalar relativistic effects and DBOC. The most accurate description of the infrared band origins of singlet CH 2 was thus achieved for the energy range where the impact of the nonadiabatic coupling due to the Renner-Teller effect can be neglected. To obtain the probabilities of the rovibrational transitions, new ab initio DMSs were constructed both for the triplet and singlet CH 2 using the CCSD(T)/aug-cc-pCVQZ approach. Finally, the absorption spectra of triplet and singlet methylene were predicted from the variationally computed line lists.