Photolysis of HCOOH monomer and dimer in solid argon: Raman characterization of in situ formed molecular complexes

Abstract

Raman spectroscopy combined with the matrix isolation technique was employed to study the 193-nm photodecomposition products of formic acid in an argon matrix. The Raman-active fundamentals belonging to the CO(2) + H(2) and CO + H(2)O photoproducts were assigned. Also, bands due to Fermi resonance between the stretching vibration (nu(1)) and the overtone of the bending mode (2nu(2)) of CO(2) were identified. Both ortho- and para-H(2) molecules were identified from their rotational lines S(0)(1) and S(0)(0), respectively. These bands appeared upon matrix annealing as well as after prolonged photolysis. Additionally, photolysis of FA dimers produces oxalic acid and its secondary photoproducts, CO(2) + CO + H(2)O. All experimental studies were supported by ab initio calculations.