Microscopic Mechanism of Proton Transfer in Pure Water Under Ambient Conditions

Abstract

 The situation in the acidic/base solution is not necessarily the same as in pure water
 The autoionization constant for water is only 10-14 under ambient condition
 To overcome this issue, they modeled periodic water box systems containing 1000
molecules for tens of nanoseconds based on NNP with quantum mechanical accuracy
 The NNP was generated by training a dataset containing the energies and atomic
forces of 17075 configurations of periodic water box systems
 These data points were calculated at the MP2 level
 They found that the size of the system and the duration of the simulation have a
significant impact on the convergence of the results
 Their simulation showed that hydronium (H3O+) and hydroxide (OH-) ions in water
have difference hydration structure, thermodynamic and kinetic properties, e.g., the
longer-lasting and more stable hydration structure of OH- ions than that of H3O+,
higher barrier energy for OH- than H3O+
 PT via H3O+ can occur among multiple molecules

Introduction
 Water molecules can self-ionize, and protons transfer from one water molecule to
other water molecules to produce hydronium (H3O+) and hydroxide (OH-) ions.
 The timescale of the PT process was estimated on the order of picoseconds by
measuring the difference between the resonance frequency of excess protons using
NMR spectroscopy.
 Previous study explained that OH- diffuses slower than H3O+ in water
 AIMD calculations are severely limited by the system size (~200 atoms) and
relatively short timescales (tens of picoseconds)
 This study focused on the PT process in pure bulk water (Scheme 1)
 They used PBC-GEBF to calculate the energy and atomic forces of periodic water
box system at MP2 level
 They trained the NNP using DeePMD-kit
 Using PBC-GEBF/DeePMD scheme, they simulated a periodic liquid water box
containing 1000 molecules on a timescale of tens of nanoseconds.
Methods
1. Quantum chemistry calculations on the periodic water box at the MP2 level using
PBD-GEBF
 The potential energy and atomic forces of each structure were calculated using
the PBC-GEBF approach implemented in LSQC program.
 They found ζ =4 Å And λ=10 worked best and MP2/6-31+G(d, p) level exhibit
balanced computational cost and accuracy
2. Training of the NNP Model Based on the PBC-GEBF/DeepMD Calculations.
 Initial sampling was generated from the system contains 64 water molecules and
the second consists of 62 water molecules plus a pair of H3O+ and OH- ions.
 They performed MD simulation with NPT ensemble (300K and 1 bar) for 10 ns
and used PBC-GEBF to compute the total energy and atomic force.
 After the NNP training, they performed parallel MD simulation on four different
initial structures containing a pair of H3O+ and OH- ions and 62 water molecules
in a 12.4 x 12.4 x 12.4 Å3 box under PBC using LAMMPS.
  They employed the maximum standard deviation (MSE)
 The 80% from 17075 configurations were randomly selected as the training set,
and the remaining data were used as the test set.
3. Classical and Quantum Simulations with NNP
 The bulk system contained one H3O+ ion and one OH- ion solvated by 998 water
molecules in 30.8 x 30.8 x 30.8 Å3 box with periodic cubic cell and was
simulated using LAMMPS.
 To determine the finite-size effects, they built model systems with a pair of
H3O+ and OH- ions added to pure water systems containing 62, 126, 254, and
510 water molecules.
 The relatively large 1000-water system sampled at a timescale of tens of
nanoseconds was adopted in the subsequent data analysis in this work.
 To account for the finite-size effects, they estimated diffusion coefficient D
4. Performance of the NNP Model
 They evaluate the accuracy of NNP with R2 value of the energy and atomic
forces and MAE for the training set.
 The calculation density was performed at 300K
 They monitored the structure of water by calculation RDF of gOwOw, gOwHw,
and gHwHw

Result and Discussion

1. Effects of size of the system and the simulation duration
 The fluctuations decrease as the system size increase in calculation temperature
(Figure 2A) and pressure (Figure 2B)
 The statistically significant fluctuations in temperature and pressure in the
relatively small systems so effect of value of density ρ and diffusion coefficient
D PBC
 The density ρ falls into a very narrow range of 1.03-1.04 g/cm3 in the 1000-water
system, much closer to the experimentally determined value of 0.997 g/cm3.
 The diffusion coefficient also convergence with increasing system size.
2. Solvation structures of H3O+ and OH-
 Position of the peaks of gO*-Ow in RDF profiles show a trend of H3O+ < Oh- <
H2O
 The H3O+ and OH- ions are more compact than H2O
 Less compact of OH- than H3O+ is likely associated with spatial repulsion
between water molecules
 The rightward shift of gO*-Hw of the hydroxide ion compared to that of the
hydronium’s peak of gO*-Ow also confirms the above observation.
3. Kinetic and Thermodynamic Factors Cause H3O+ to Be More Prone to Proton
Transfer. Than OH-
 O-H bone is broken if the distance exceeds 1.3 Å
 Reorganizing the hydration layer structure time labeled as the residence time
(considered the eigen state), while the time for PT, that is, from breaking O-H
bond up to formation a new O-H bond labeled as PT time (considered the Zundel
state)
4. Multiple Successive PT Processes Are More Likey to Ocuu via H3O+ Rather Than
via OH-