Photodissociation of formic acid

Abstract

The photodissociation of formic acid has been studied experimentally and theoretically. Ab initio calculations were performed to study the dissociative profiles of five reaction channels on the S0, S1, and T1 potential energy surfaces. The vibrationally excited nascent products were detected using a time-resolved Fourier transform infrared spectrometer after laser photolysis at 248 or 193 nm. In the 248 nm photolysis, the HCOOH molecule was first excited to the S1 state, but it was found that the dissociation takes place on the S0 surface after internal conversion. The products of the vibrationally excited CO, CO2(v3) and H2O(v1) were detected. During the dissociation process the vibrationally energized molecule is geometrically memorized and dynamically controlled, with the yield preference of CO and H2O over that of CO2 and H2. The ratio of CO(v⩾1)/CO2(v⩾1) is estimated as <7.5. Vibrationally excited CO (v) and CO2(v3) are also found in the 193 nm photolysis but the CO/CO2 ratio increases to 11. Most of the dissociation is thought to occur on the S0 state. At this wavelength another dissociation channel which produces OH and HCO radicals on S1 surface has been identified. The dissociation is unlikely to occur on the T1 surface, as the energy barriers are fairly high.