cis-trans formic acid dimer: experimental observation and improved stability against proton tunneling.

We prepared the first cis-trans dimer of formic acid and measured its vibrational spectrum in a low-temperature Ar matrix. This preparation was done by selective vibrational excitation of the trans-trans noncyclic dimer. It was found that the stability of the cis-trans dimer against proton tunneling is strongly improved compared to the monomer, especially at elevated temperatures (>30 K). This surprising phenomenon was explained by differences in dynamical, energetic, and vibrational properties of the dimer and monomer. The obtained results show that the proton tunneling reactions can be strongly modified in the hydrogen-bonded solid network compared to the monomeric species.