Confirmation of gaseous methanediol from state-of-the-art theoretical rovibrational characterization

Abstract

High-level rovibrational characterization of methanediol, the simplest geminal diol, using state-of-the-art, purely ab initio techniques unequivocally confirms previously reported gas phase preparation of this simplest geminal diol in its C₂ conformation. The F12-TZ-cCR and F12-DZ-cCR quartic force fields (QFFs) utilized in this work are among the largest coupled cluster-based anharmonic frequencies computed to date, and they match the experimental band origins of the spectral features in the 980–1100 cm⁻¹ range to within 3 cm⁻¹, representing a significant improvement over previous studies. The simulated spectrum also matches the experimental spectrum in the strong Q branch feature and qualitative shape of the 980–1100 cm⁻¹ region. Additionally, the full set of rotational constants, anharmonic vibrational frequencies, and quartic and sextic distortion constants are provided for both the lowest energy C₂ conformer as well as the slightly higher C_s conformer. Several vibrational modes have intensities of 60 km mol⁻¹ or higher, facilitating potential astronomical or atmospheric detection of methanediol or further identification in laboratory work especially now that gas phase synthesis of this molecule has been established.