Abstract
Rotationally resolved spectra of h2- and d1-formic acid embedded in liquid helium droplets have been recorded in the spectral region of the O–H (ν1) and C–H (ν2) stretch vibrations. Accidental resonant mixing between the ν1-band of h2-formic acid and the combination bands (ν2+ν7) and (ν2+ν9) has been observed. The fundamental ν1 band can interact via Fermi resonance with the (ν2+ν7), and the (ν2+ν7) via Coriolis coupling with the (ν2+ν9) band. Examination of the resonance induced line-broadening effects suggests that the helium environment modifies vibrational relaxation dynamics. The 2ν3 C=O stretch overtone is also observed and was assigned by a density functional theory (DFT) ab initio calculation. The spectroscopic constants are determined by fitting all spectra with a standard gas phase Hamiltonian.
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