Shifting formic acid dimers into perspective: vibrational scrutiny in helium nanodroplets.

A metastable dimer of formic acid has been prepared inside superfluid helium nanodroplets and examined using IR spectroscopy and quantum chemical calculations. This dimer has one strong O-HMIDLINE HORIZONTAL ELLIPSISO & xe001;C hydrogen bond and one weak C & xe001;OMIDLINE HORIZONTAL ELLIPSISH-C bond, which is the same bonding motif that exists between adjacent molecules in catemer chains found in the crystalline phase. The strongly bound OH stretching vibration of the metastable dimer shows clear evidence of significant coupling to other vibrational modes, but it is far less extensive than that seen for the doubly hydrogen bonded global energy minimum dimer structure, which dominates in the gas phase but is not observed in helium droplets. The width and shape of the resonance pattern can be qualitatively reproduced by B3LYP-D3(BJ)/aVTZ VPT2 calculations, if additional intensity scaling is applied. However, it is the MP2/aVTZ level of theory that consistently provides the closest agreement between calculated (VPT2) and experimental frequencies for the OH stretching vibration in the formic acid monomer and metastable dimer.