Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde Cations

New high-level ab initio quartic force field (QFF) methods are explored which provide spectroscopic data for the electronically excited states of the carbon monoxide, water, and formaldehyde cations, sentinel species for expanded, recent cometary spectral analysis. QFFs based on equation-of-motion ionization potential (EOM-IP) with a complete basis set extrapolation and core correlation corrections provide assignment for the fundamental vibrational frequencies of the (A) over tilde B-2(1) and (B) over tilde (2)A(1) states of the formaldehyde cation; only three of these frequencies have experimental assignment available. Rotational constants corresponding to these vibrational excitations are also provided for the first time for all electronically excited states of both of these molecules. EOM-IP-CCSDT/CcC computations support tentative re-assignment of the nu(1) and nu(3) frequencies of the (B) over tilde (2)B2 state of the water cation to approximately 2409.3 cm(-1) and 1785.7 cm(-1), respectively, due to significant disagreement between experimental assignment and all levels of theory computed herein, as well as work by previous authors. The EOM-IP-CCSDT/CcC QFF achieves agreement to within 12 cm(-1) for the fundamental vibrational frequencies of the electronic ground state of the water cation compared to experimental values and to the high-level theoretical benchmarks for variationally-accessible states. Less costly EOM-IP based approaches are also explored using approximate triples coupled cluster methods, as well as electronically excited state QFFs based on EOM-CC3 and the previous (T)+EOM approach. The novel data, including vibrationally corrected rotational constants for all states studied herein, provided by these computations should be useful in clarifying comet evolution or other remote sensing applications in addition to fundamental spectroscopy.

Automated summary

This study explores new high-level ab initio quartic force field (QFF) methods that provide spectroscopic data for the electronically excited states of carbon monoxide, water, and formaldehyde cations, which are important in cometary spectral analysis. The QFFs based on equation-of-motion ionization potential (EOM-IP) achieve accurate assignments for the vibrational frequencies of the excited states of the formaldehyde cation. The study also proposes re-assignments for the vibrational frequencies of the water cation based on computational results.