The Gas-Phase Hydrogen Bond Complexes between Formic Acid with Hydroxyl Radical: A Theoretical Study

摘要

We report a theoretical study on seven radical hydrogen bond complexes between syn-HCOOH and OH and eight radical hydrogen bond complexes between anti-HCOOH and OH, that have been carried out by using the B3 LYP, MP2, QCISD, and CCSD(T) theoretical approaches with the 6-311+G(2df,2p) basis set. In all cases, the bonding features were analysed using the atoms in molecules (AIM) theory by Bader and the natural bond orbital (NBO) partition scheme by Weinhold et al. We have found twelve complexes having a single hydrogen bond and three complexes presenting a cyclic structure with multiple bonds, pointing out the existence of a cooperative effect. One of them presents a bound OO interaction producing a stabilisation effect. The stability of these complexes has been calculated to be in the -0.81 and -5.96 kcal mol~(-1) range and their possible implication in the HCOOH plus OH reaction is also discussed. Finally, we also report the computed harmonic vibrational frequencies of the two O-H stretching modes and the HOC out-of-plane wagging mode, along with the frequency red-shifts originated by the complex formation and the corresponding computed intensity ratio relative to the monomers.