Potential energy profile for the Cl + (H2O)3 → HCl + (H2O)2OH reaction. A CCSD(T) study

Abstract

Four different reaction pathways are initially located for the reaction of Cl atom plus water trimer Cl + (H₂O)₃ → HCl + (H₂O)₂OH using a standard DFT method. As found for the analogous fluorine reaction, the geometrical and energetic results for the four chlorine pathways are closely related. However, the energetics for the Cl reaction are very different from those for fluorine. In the present paper, we investigate the lowest-energy chlorine pathway using the “gold standard” CCSD(T) method in conjunction with correlation-consistent basis sets up to cc-pVQZ. Structurally, the stationary points for the water trimer reaction Cl + (H₂O)₃ may be compared to those for the water monomer reaction Cl + H₂O and water dimer reaction Cl + (H₂O)₂. Based on the CCSD(T) energies, the title reaction is endothermic by 19.3 kcal mol⁻¹, with a classical barrier height of 16.7 kcal mol⁻¹ between the reactants and the exit complex. There is no barrier for the reverse reaction. The Cl⋯(H₂O)₃ entrance complex lies 5.3 kcal mol⁻¹ below the separated reactants. The HCl⋯(H₂O)₂OH exit complex is bound by 8.6 kcal mol⁻¹ relative to the separated products. The Cl + (H₂O)₃ reaction is somewhat similar to the analogous Cl + (H₂O)₂ reaction, but qualitatively different from the Cl + H₂O reaction. It is reasonable to expect that the reactions between the chlorine atom and larger water clusters may be similar to the Cl + (H₂O)₃ reaction. The potential energy profile for the Cl + (H₂O)₃ reaction is radically different from that for the valence isoelectronic F + (H₂O)₃ system, which may be related to the different bond energies between HCl and HF.