OH-stretch overtone of methanol: empirical assignment using a two temperature technique in a supersonic jet

This paper describes a novel approach for empirical lower state assignments in complex high resolution ro-vibrational overtone spectra of molecules with low rotational constants and complex intramolecular dynamics. Methanol, CH3OH, was chosen as a representative of such molecules - it is an asymmetric top with two non-hydrogen nuclei and hindered internal rotation leading to dense and disordered rotational structure of vibrational overtone bands. We report the first rotationally resolved methanol spectra of the OH-stretch overtone 2ν1 band using sub-Doppler diode laser spectroscopy in a supersonic jet, and describe how the combination of two temperature analysis (TTA) and analysis by ground state combination differences (GSCDs) is used to reliably identify spectral lines that originate from lowest rotational states. In the first step of the analysis, the TTA was utilized to obtain a set of possible rotational assignments for each spectral line using the line intensity variation between two different temperatures in the supersonic jet (13, and 56 K respectively). Thereafter, the GSCDs were used to confirm specific lower state assignment for those spectral lines that have been identified to have low rotational ground states by the TTA. We show that the TTA pre-selection leads to fast and reliable confirmation by GSCDs and avoids false assignments due to accidental GSCD matches. The procedure yields an important subset of reliably assigned spectral lines in the complex ro-vibrational structure that provides a convenient starting point for subsequent application of traditional spectral analysis techniques.