期刊
CHEMPHYSCHEM
卷 21, 期 20, 页码 2334-2346出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.202000498
关键词
ab initio molecular dynamics; dielectric relaxation spectroscopy; electrolyte solutions; hydration number; water orientational dynamics
资金
- National Research Foundation of Korea (NRF) through the Korea government (MSIP) [2016R1A3B1908336]
- Department for Business, Energy and Industrial Strategy (BEIS) [294766]
- NERC research council
- EPSRC research council
- QMUL Principal's Postgraduate Research Studentships
- EPSRC [EP/P020194/1, EP/L000202]
- QMUL Research-IT
- EPSRC [EP/P020194/1] Funding Source: UKRI
- National Research Foundation of Korea [2016R1A3B1908336] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
We present an atomistic simulation scheme for the determination of the hydration number (h) of aqueous electrolyte solutions based on the calculation of the water dipole reorientation dynamics. In this methodology, the time evolution of an aqueous electrolyte solution generated fromab initiomolecular dynamics simulations is used to compute the reorientation time of different water subpopulations. The value ofhis determined by considering whether the reorientation time of the water subpopulations is retarded with respect to bulk-like behavior. The application of this computational protocol to magnesium chloride (MgCl2) solutions at different concentrations (0.6-2.8 mol kg(-1)) giveshvalues in excellent agreement with experimental hydration numbers obtained using GHz-to-THz dielectric relaxation spectroscopy. This methodology is attractive because it is based on a well-defined criterion for the definition of hydration number and provides a link with the molecular-level processes responsible for affecting bulk solution behavior. Analysis of theab initiomolecular dynamics trajectories using radial distribution functions, hydrogen bonding statistics, vibrational density of states, water-water hydrogen bonding lifetimes, and water dipole reorientation reveals that MgCl(2)has a considerable influence on the hydrogen bond network compared with bulk water. These effects have been assigned to the specific strong Mg-water interaction rather than the Cl-water interaction.
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