The Reaction between Bromine and the Water Dimer and the Highly Exothermic Reverse Reaction

The entrance complex, transition state, and exit complex for the bromine atom plus water dimer reaction Br + (H 2 O) 2 → HBr + (H 2 O)OH and its reverse reaction have been investigated using the CCSD(T) method with correlation consistent basis sets up to cc‐pVQZ‐PP. Based on the CCSD(T)/cc‐pVQZ‐PP results, the reaction is endothermic by 31.7 kcal/mol. The entrance complex Br⋯(H 2 O) 2 is found to lie 6.5 kcal/mol below the separated reactants. The classical barrier lies 28.3 kcal/mol above the reactants. The exit complex HBr⋯(H 2 O)OH is bound by 6.0 kcal/mol relative to the separated products. Compared with the corresponding water monomer reaction Br + H 2 O → HBr + OH, the second water molecule lowers the relative energies of the entrance complex, transition state, and exit complex by 3.0, 3.8, and 3.7 kcal/mol, respectively. Both zero‐point vibrational energies and spin‐orbit coupling effects make significant changes to the above classical energetics. Including both effects, the predicted energies relation to separated Br + (H 2 O) 2 are −3.0 kcal/mol [Br···(H 2 O) 2 ], 28.2 kcal/mol [transition state], 26.4 kcal/mol [HBr···(H 2 O)OH], and 30.5 kcal/mol [separated HBr + (H 2 O)OH]. The potential energy surface for the Br + (H 2 O) 2 reaction is related to that for the valence isoelectronic Cl + (H 2 O) 2 system but radically different from the F + (H 2 O) 2 system. © 2015 Wiley Periodicals, Inc.