Born−Oppenheimer ab Initio QM/MM Dynamics Simulations of Na⁺and K⁺in Water:  From Structure Making to Structure Breaking Effects

The description of nonadditive contributions in the first hydration shell of Na + and K + has been improved by performing molecular dynamics simulations based on combined ab initio quantum mechanical and molecular mechanical potentials. The active-site region, the first hydration sphere of ions, is treated by Born−Oppenheimer ab initio quantum mechanics, while the environment is described by classical pair potentials. The average coordination numbers obtained by this high accuracy method, with valence double-ζ basis sets for water and Los Alamos ECP plus DZ basis sets for cations, lead to a lower value of 5.6 ± 0.3 for Na + and a higher value of 8.3 ± 0.3 for K +, respectively, compared to the corresponding values of 6.5 ± 0.2 and 7.8 ± 0.2 resulting from pair potentials. The effects of nonadditive terms are also found to play a significant role in the preferential orientation of water molecules within the first hydration shell of Na + and K + . The experimentally observed “structure-breaking” effects of K + are well reflected and explained on a molecular basis by the simulation results.