An Ab Initio Quantum Mechanical Charge Field Molecular Dynamics Simulation of a Dilute Aqueous HCl Solution

作者：Kritayakornupong Chinapong^*; Vchirawongkwin Viwat; Rode Bernd M

来源：Journal of Computational Chemistry, 2010, 31(8): 1785-1792.

DOI：10.1002/jcc.21469

• hydrogen chloride
• hydration structure
• dynamical properties
• hydrogen bond
• acid dissociation
• proton transfer
• simulation
• QMCF

An ab initio quantum mechanical charge field (QMCF) molecular dynamics simulation has been performed to study the structural and dynamical properties of a dilute aqueous HCl solution. The solute molecule HCl and its surrounding water molecules were treated at Hartree-Fock level in conjunction with Dunning double-zeta plus polarization function basis sets. The simulation predicts an average H-Cl bond distance of 1.28 angstrom. which is in good agreement with the experimental value. The H(HCl)center dot center dot center dot O(w). and Cl(HCl)center dot center dot center dot H(w), distances of 1.84 and 3.51 angstrom were found for the first hydration shell. At the hydrogen site of HCl, a single water molecule is the most preferred coordination, whereas an average coordination number of 12 water molecules of the full first shell was observed for the chloride site. The hydrogen bonding at the hydrogen site of HCl is weakened by proton transfer reactions and an associated lability of ligand binding. Two proton transfer processes were observed in the QMCF MD simulation, demonstrating acid dissociation of HCl. A weak structure-making/breaking effect of HCl in water is recognized from the mean residence times of 2.1 and 0.8 ps for ligands in the neighborhood of Cl and H sites of HCl, respectively.

• 出版日期2010-6