Predicting the Ionic Product of Water

摘要: We present a first-principles calculation and mechanistic characterization of the ion product liquid water (K W ), based on Quantum Cluster Equilibrium (QCE) theory with variety ab initio density functional methods. The QCE method is T-dependent Boltzmann weighting different-sized clusters consequently enables observation thermodynamically less favored therefore low populated species such as hydronium hydroxide ions in water. find that common quantum chemical methods achieve semi-quantitative accuracy predicting K its T-dependence. Dominant ion-pair equilibrium distribution are found to exhibit stable 2-coordinate buttress-type motifs, all maximally Grotthus-ordered H-bond patterns successfully prevent recombination at 3-coordinate bridgehead sites. employ standard chemistry techniques describe kinetic aspects formation, we obtain NBO-based bonding indices characterize other electronic, structural, spectroscopic, reactive properties cluster-mediated ionic dissociation.