title: Interaction of formic acid with nitrogen: stabilization of the higher-energy conformer.
abstract: Conformational change is an important concept in chemistry and physics. In the present work, we study conformations of formic acid (HCOOH, FA) and report the preparation and identification of the complex of the higher-energy conformer cis-FA with N(2) in an argon matrix. The cis-FA···N(2) complex was synthesized by combining annealing and vibrational excitation of the ground-state trans-FA in a FA/N(2)/Ar matrix. The assignment is based on IR spectroscopic measurements and ab initio calculations. The cis-FA···N(2) complex decay in an argon matrix is much slower compared with the cis-FA monomer. In agreement with the experimental observations, the calculations predict a substantial increase in the stabilization barrier for the cis-FA···N(2) complex compared with the uncomplexed cis-FA monomer. A number of solvation effects in an argon matrix are computationally estimated and discussed. The present results on the cis-FA···N(2) complex show that intermolecular interaction can stabilize intrinsically unstable conformers, as previously found for some other cis-FA complexes.
authors.affiliation: Department of Chemistry, P.O. Box 55, FIN-00014 University of Helsinki, Finland. kseniya.marushkevich@helsinki.fi
authors.forename: Kseniya
authors.initials: K
authors.lastname: Marushkevich
authors.forename: Markku
authors.initials: M
authors.lastname: Räsänen
authors.forename: Leonid
authors.initials: L
authors.lastname: Khriachtchev
mesh_terms: D001128:Argon / Q000737:chemistry; D005561:Formates / Q000737:chemistry*; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D009584:Nitrogen / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D005561:Formates; C030544:formic acid; D001128:Argon; D009584:Nitrogen