Hyperfine structure in the rotational spectra of trans-formic acid: Lamb-dip measurements and quantum-chemical calculations

Abstract

Context. Formic acid, HCOOH, is the simplest organic acid and the first that has been identified in the interstellar medium. Its astrophysical relevance has motivated this spectroscopic study. Aims. The aim of this investigation is to provide very accurate rest frequencies for the trans isomer of HCOOH as well as to improve the spectroscopic and hyperfine parameters available in the literature for this molecule. Methods. The Lamb-dip technique has been exploited in order to record the rotational spectrum of trans-HCOOH at sub-Doppler resolution in the millimeter- and submillimeter-wave frequency ranges and, when possible, to resolve the hyperfine structure due to the hydrogen nuclei. THz measurements have been carried out as well. The experimental investigation has been supported by high-level quantum-chemical calculations. Results. As a consequence, we report here the most accurate ground-state rotational parameters known so far for the main isotopic species of trans-HCOOH as well as an accurate and reliable set of hyperfine parameters. Conclusions. The improvement in the accuracy of the ground-state rotational and hyperfine parameters as well as of the rest frequencies of rotational transitions might therefore be useful for future radioastronomical observations.