Increasing the weights in the molecular work-out of - and -formic acid: extension of the vibrational database deuteration.

The higher-energy cis- as well as the global minimum trans-rotamers of the four H/D isotopologues of the formic acid monomer have been examined with Raman jet spectroscopy extending the vibrational gas phase reference database by eleven new cis-band positions for HCOOD, DCOOH, and DCOOD. With these new additions, all O-H/D, C-H/D, and C[double bond, length as m-dash]O stretching as well as the O-D in-plane bending vibrations of these higher-energy rotamers are known in addition to the previously determined C-O stretch and OH torsion of cis-HCOOH. Further, a comparison of the vibrational spectra of all four H/D isotopologues of the globally stable trans-rotamer of formic acid is shown to be very helpful in revealing similarities and differences in these systems, particularly with regard to Fermi resonances. Amongst the most prominent ones is the ν5/2ν9 resonance doublet of trans-HCOOH, for which we provide more insight into a recently suggested label switch of the resonance partners via the comparison of infrared and Raman jet spectra.