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Water structure, dynamics, and vibrational spectroscopy in sodium bromide solutions
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10.1063/1.3242083
/content/aip/journal/jcp/131/14/10.1063/1.3242083
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/14/10.1063/1.3242083

Figures

Image of FIG. 1.
FIG. 1.

Theoretical ( is or ) radial distribution functions.

Image of FIG. 2.
FIG. 2.

Theoretical (Th) and experimental (Exp) (Ref. 71) second-order orientational time-correlation functions for water molecules in pure water and aqueous NaBr solutions. is the second-order Legendre polynomial; is the unit vector along the OH bond (OD bond of the dilute HOD molecules in experiment).

Image of FIG. 3.
FIG. 3.

Calculated OD-stretch frequencies for clusters and point charges of surrounding molecules, vs the electric field on the D, projected along the OD vector. 99 randomly chosen data points (out of 999) are shown in this figure. The frequency map is the red curve. The rms deviation between the map and data points is .

Image of FIG. 4.
FIG. 4.

Experimental (Ref. 71) (upper panel) and theoretical (two lower panels) line shapes for the OD stretch of HOD in pure water (in black), concentrated NaCl (in red) and NaBr (in green) solutions. The background-subtracted FTIR spectrum of the OD stretch in concentrated NaCl (5.4 M NaCl in 5% ) was taken by the authors. The experimental for the OD stretch of HOD in pure water is used for the line shape calculations for pure water; the experimental for the concentrated NaBr solution is used in the calculations for both concentrated NaCl and NaBr solutions (Ref. 71). The middle panel shows theoretical curves calculated using , and the lower panel shows theoretical curves calculated using . The theoretical black curves for pure water in the two lower panels are the same.

Image of FIG. 5.
FIG. 5.

Calculated OD-stretch frequencies and dipole derivatives for clusters sampled from a simulation of concentrated NaCl solution, vs effective electric field on the D atom, projected along the OD vector. The red curves are the maps.

Image of FIG. 6.
FIG. 6.

Experimental (Ref. 71) and theoretical line shapes for the OD stretch of HOD in pure water and aqueous NaBr solutions. The experimental ’s are used in the line shape calculations (Ref. 71)

Image of FIG. 7.
FIG. 7.

Theoretical and experimental (Ref. 71) normalized FTCFs for the OD stretch of HOD in pure water and aqueous NaBr solutions.

Image of FIG. 8.
FIG. 8.

Calculated frequency distributions, spectral densities and line shapes for the OD stretch of HOD in pure water and 5.9 M NaBr solution.

Image of FIG. 9.
FIG. 9.

Distributions of OD-stretch frequencies (top panel) and spectral densities (bottom panel) for different hydrogen-bonding classes for the OD stretch of HOD in pure water and aqueous NaBr solutions. Dashed lines are for class W, dotted lines for class A, and solid lines for class F. Black is for pure water, red is for 1.8 M, green is for 3.1 M, and blue is for 5.9 M.

Image of FIG. 10.
FIG. 10.

Theoretical normalized TCFs for pure water and aqueous NaBr solutions, up to 10 ps. Solid lines are the frequency TCFs, and dashed lines are the NTCFs (see text). Black is for pure water, red is for 1.8 M, green is for 3.1 M, and blue is for 5.9 M.

Image of FIG. 11.
FIG. 11.

Theoretical normalized TCFs for pure water and aqueous NaBr solutions, up to 40 ps. Solid lines are the FTCFs (black is pure water, red is for 1.8 M, green is for 3.1 M, and blue is for 5.9 M). The dashed, dot-dash, and dotted red lines, are for the D, , and NTCFs, respectively, for the 1.8 M solution.

Image of FIG. 12.
FIG. 12.

Theoretical spectral densities for different solvation shells, normalized to peak height.

Image of FIG. 13.
FIG. 13.

Relaxation to equilibrium of the average OD-stretch frequencies for different subensembles of water molecules, based on ionic solvation shells.

Image of FIG. 14.
FIG. 14.

Theoretical rotational anisotropy TCFs for different solvation shells.

Tables

Generic image for table
Table I.

Overview of the MD simulations. and are the number of water molecules and ion pairs, respectively. Box size is calculated using the experimental densities.120,121

Generic image for table
Table II.

Potential parameters used in the MD simulations. The Lorentz–Berthelot combination rules are used to determine the intermolecular Lennard-Jones interactions between different atom types.122

Generic image for table
Table III.

Relationships for the transition frequency (in ), dipole derivative (normalized by the gas-phase value ), and 1–0 matrix element of the OD-stretching coordinate (in Å). is the electric field (in atomic units) on the D atom projected along the OD bond. The correlation coefficient and rms error of each fit are listed.

Generic image for table
Table IV.

Summary of theoretical (Th), using and approaches, and experimental (Exp) line shapes for pure water, and concentrated aqueous NaCl and NaBr solutions. Peak position, shift in peak position from pure water, and FWHM are all in .

Generic image for table
Table V.

Summary of theoretical (Th) and experimental (Exp) (Ref. 71) line shapes for pure water and aqueous NaBr solutions of various concentrations. Peak position, shift in peak position from pure water, and FWHM are all in .

Generic image for table
Table VI.

Summary of calculated frequency distributions and spectral densities of the OD stretch of HOD in pure water and aqueous NaBr solutions. Both peak position and FWHM are in .

Generic image for table
Table VII.

Summary of the populations, , of the three hydrogen-bonding classes (F, W, A) for the D atom of HOD in pure water and aqueous NaBr solutions.

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/content/aip/journal/jcp/131/14/10.1063/1.3242083
2009-10-13
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Water structure, dynamics, and vibrational spectroscopy in sodium bromide solutions
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/14/10.1063/1.3242083
10.1063/1.3242083
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