Intramolecular vibrational redistribution in formic acid and its deuterated forms

International audienceThe intramolecular vibrational relaxation dynamics of formic acid and its deuterated isotopologues is simulated on the full-dimensional potential energy surface of Richter and Carbonnière [J. Chem. Phys. 148, 064303 (2018)] using the Heidelberg MCTDH package. We focus on couplings with the torsion vibrational modes close to the trans– cis isomerization coordinate from the dynamics of artificially excited vibrational mode overtones. The bright C–O stretch vibrational mode is coupled to the out-of-the plane torsion mode in HCOOH, where this coupling could be exploited for laser-induced trans-to- cis isomerization. Strong isotopic effects are observed: deuteration of the hydroxyl group, i.e., in HCOOD and DCOOD, destroys the C–O stretch to torsion mode coupling whereas in DCOOH, little to no effect is observed