jp6b05821_si_001.pdf (372.26 kB)
Toward Realistic Transfer Rates within the Coupled Molecular Dynamics/Lattice Monte Carlo Approach
journal contribution
posted on 2016-08-22, 00:00 authored by Gabriel Kabbe, Christian Dreßler, Daniel SebastianiWe
refine our recently developed coupled molecular dynamics/lattice
Monte Carlo (cMD/LMC) scheme for the simulation of protonation dynamics
in complex hydrogen-bonded solids in view of improving the resulting
transport processes. The distance dependency of the proton jump rate
between lattice sites and its dependence on additional geometric criteria
(bond angles) are derived in a systematic and consistent way. The
distance dependency follows an accurate potential energy surface (PES)
scan from quantum chemical calculations. The novel geometric criterion
takes into account that proton hopping occurs almost exclusively along
linear hydrogen bonds. We illustrate the capabilities and the versatility
of our scheme on the example of two chemically quite different condensed
phase systems: a crystalline solid acid compound and a liquid crystal.
Surprisingly, we find that our cMD/LMC scheme yields converged mobility
parameters even when based on underlying ab initio molecular dynamics (AIMD) trajectories which themselves are not
fully converged. Our method yields more accurate values for the mean
square displacement, the OH bond autocorrelation function and the
proton jump frequencies in agreement with both reference AIMD simulations
and experimental values.
History
Usage metrics
Categories
Keywords
resulting transport processesquantum chemical calculationsproton jump rateproton jump frequenciesmean square displacementadditional geometric criteriaab initio lattice monte carloreference aimd simulationsdistance dependency followscoupled molecular dynamicsdistance dependencymolecular dynamicslattice sitesprotonation dynamicsmethod yieldsliquid crystalfully convergedexperimental valuesconsistent waycomplex hydrogenbonded solidsbond anglesaccurate values
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC