+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Ab Initio Molecular Dynamics Study of a Highly Concentrated LiCl Aqueous Solution

Ab Initio Molecular Dynamics Study of a Highly Concentrated LiCl Aqueous Solution

Journal of Chemical Theory and Computation 4(7): 1040-1048

The properties of a highly concentrated aqueous lithium chloride solution (|LiCl| = 14 mol L(-1)) are investigated using Car-Parrinello molecular dynamics. The coordination spheres of lithium ions, chloride ions, and water molecules are described successively. On the whole, our simulation provides results-distances and coordination numbers-in very good agreement with experimental data. The lithium solvation shell is found to exhibit a tetrahedral configuration on average, with three stable clusters observed during the simulation: Li(+)-4H2O, Li(+)(H2O)3Cl(-), and Li(+)(H2O)2(Cl(-))2. The chloride coordination sphere is logically formed by strong Cl-H hydrogen bonds with neighboring water molecules, for a mean coordination number of 4.4. The structuring of water molecules is strongly affected by the high concentration in LiCl. The hydrogen bond network is globally broken down, but little variation is calculated on water dipoles (μ = 3.07 D) because of the strong polarization from Li(+) and Cl(-) ions. We also point out some of the characteristic features of such a highly concentrated solution: water bridging between Li(+) and Cl(-) hydration spheres, Li(+)-Cl(-) ion-pairing, and intermediate behavior between dilute solutions and molten salts. Finally, the reliability of our simulation to describe ion-pairing is discussed.

Please choose payment method:

(PDF emailed within 0-6 h: $19.90)

Accession: 057111973

Download citation: RISBibTeXText

PMID: 26636357

DOI: 10.1021/ct800007v

Related references

Molecular dynamics study of the coordination sphere of trivalent lanthanum in a highly concentrated LiCl aqueous solution: a combined classical and ab initio approach. Journal of Physical Chemistry. B 112(34): 10603-7, 2008

Contributions to the chemistry of highly concentrated aqueous electrolyte solutions. XXV. Ionophoretic investigation of the association of Al3+, Sc3+, Ga3+ and In3+ ions in concentrated solutions of NaClO4 and LiCl. Collection of Czechoslovak Chemical Communications 36(12): 3891-3899, 1971

Structure and dynamics of the CrIII ion in aqueous solution: Ab initio QM/MM molecular dynamics simulation. Journal of Computational Chemistry 25(13): 1576-1583, 2004

Structure and Dynamics of the Cd 2+ Ion in Aqueous Solution: Ab Initio Qm/Mm Molecular Dynamics Simulation. The Journal of Physical Chemistry A 107(48): 10330-10334, 2003

Structure and dynamics of the [Zn(NH3)(H2O)5]2+ complex in aqueous solution obtained by an ab initio QM/MM molecular dynamics study. Physical Chemistry Chemical Physics 8(14): 1675-1681, 2006

Structure and dynamics of the U4+ ion in aqueous solution: an ab initio quantum mechanical charge field molecular dynamics study. Inorganic Chemistry 48(9): 3993-4002, 2009

Ionic solvation and association in LiCl aqueous solution: a density functional theory, polarised continuum model and molecular dynamics investigation. Molecular Physics 112(12): 1710-1723, 2014

Erbium(III) in aqueous solution: an ab initio molecular dynamics study. Journal of Physical Chemistry. B 117(48): 15151-6, 2013

Investigation of the structure of concentrated aqueous solution of LiCl at low temperatures by the method of integral equations. Russian Chemical Bulletin 48(10): 1858-1863, 1999

High-Order Ca(II)-Chloro Complexes in Mixed CaCl2-LiCl Aqueous Solution: Insights from Density Functional Theory and Molecular Dynamics Simulations. Journal of Physical Chemistry. a 120(28): 5635-5648, 2016

Ab initio molecular dynamics study of ascorbic acid in aqueous solution. Molecular Physics 105(1): 17-23, 2007

The Jahn-Teller effect of the Cr(2+) ion in aqueous solution: Ab initio QM/MM molecular dynamics simulations. Journal of Computational Chemistry 29(1): 115-121, 2008

Ab initio molecular dynamics study of an aqueous NaCl solution under an electric field. Physical Chemistry Chemical Physics 18(33): 23164-23173, 2016

Deprotonation of a histidine residue in aqueous solution using constrained ab initio molecular dynamics. Journal of the American Chemical Society 124(45): 13380, 2002

Carbon dioxide capture in 2,2'-iminodiethanol aqueous solution from ab initio molecular dynamics simulations. Journal of Chemical Physics 149(22): 224103, 2018