Probing water dynamics with OH

Abstract Isotropic Raman spectra of aqueous solutions of LiOH, NaOH and KOH at concentrations ranging from high dilution to saturation have been measured and the frequency and width of the OH − stretching band have been analyzed. The dependence of the bandwidth on solute concentration suggests that the OH − vibration undergoes a transition from fast to slow modulation regimes as the solvent concentration decreases below the value of ∼20 water molecules per solute molecule. A correlation between this finding and structural modifications of the H-bond network of the solvent at similar concentrations is envisaged.

[1]  H. Kagi,et al.  Changes in the structure of water deduced from the pressure dependence of the Raman OH frequency. , 2004, The Journal of chemical physics.

[2]  M. Klein,et al.  First-principles study of aqueous hydroxide solutions. , 2002, Journal of the American Chemical Society.

[3]  M. Arai,et al.  AN IN SITU RAMAN SPECTROSCOPY STUDY OF SUBCRITICAL AND SUPERCRITICAL WATER: THE PECULIARITY OF HYDROGEN BONDING NEAR THE CRITICAL POINT , 1998 .

[4]  G. Walrafen,et al.  Raman spectra from very concentrated aqueous NaOH and from wet and dry, solid, and anhydrous molten, LiOH, NaOH, and KOH. , 2006, The Journal of chemical physics.

[5]  A. Soper,et al.  Ions in water: The microscopic structure of concentrated hydroxide solutions RID C-6410-2008 , 2004 .

[6]  Yusuke Jin,et al.  Near-infrared spectroscopic study of water at high temperatures and pressures , 2003 .

[7]  A. Soper,et al.  Ions in water: the microscopic structure of concentrated hydroxide solutions. , 2005, The Journal of chemical physics.

[8]  A. Soper,et al.  Solvation of hydroxyl ions in water , 2003 .

[9]  P. Roy,et al.  Signatures of the hydrogen bonding in the infrared bands of water. , 2005, The Journal of chemical physics.

[10]  Dominik Marx,et al.  Proton transfer 200 years after von Grotthuss: insights from ab initio simulations. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[11]  D. Oxtoby Dephasing of Molecular Vibrations in Liquids , 2007 .

[12]  D. Combes,et al.  Effect of salts on dynamics of water: A Raman spectroscopy study , 1990 .

[13]  Felix Franks,et al.  Water:A Comprehensive Treatise , 1972 .

[14]  Alain H. Roux,et al.  Capacités calorifiques, volumes, expansibilités et compressibilités des solutions aqueuses concentrées de LiOH, NaOH et KOH , 1984 .

[15]  M. Parrinello,et al.  Solvated excess protons in water: quantum effects on the hydration structure , 2000 .

[16]  A. Soper Tests of the empirical potential structure refinement method and a new method of application to neutron diffraction data on water , 2001 .

[17]  W.-H. Yang,et al.  Raman isosbestic points from liquid water , 1986 .

[18]  H. Thirsk,et al.  Proton transfer conductance in aqueous solution. Part 1.—Conductance of concentrated aqueous alkali metal hydroxide solutions at elevated temperatures and pressures , 1971 .

[19]  E. P. Perman,et al.  Vapour pressure and heat of dilution.—Part VII. Vapour pressures of aqueous solutions of sodium hydroxide and of alcoholic solutions of calcium chloride , 1931 .

[20]  Jean-Joseph Max,et al.  Isotope effects in liquid water by infrared spectroscopy , 2002 .

[21]  P. Sipos,et al.  Viscosities and Densities of Highly Concentrated Aqueous MOH Solutions (M+ = Na+, K+, Li+, Cs+, (CH3)4N+) at 25.0 °C , 2000 .

[22]  A. Zwick,et al.  Effect of High Hydrostatic Pressure and Additiveson the Dynamics of Water: a Raman SpectroscopyStudy , 1996 .

[23]  W. Kunz,et al.  Vapor Pressures and Osmotic Coefficients of Aqueous LiOH Solutions at Temperatures Ranging from 298.15 to 363.15 K , 2005 .

[24]  A. Soper,et al.  Structural characterization of NaOH aqueous solution in the glass and liquid states , 2001 .

[25]  Alan K. Soper,et al.  The radial distribution functions of water and ice from 220 to 673 K and at pressures up to 400 MPa , 2000 .

[26]  Jean-Joseph Max,et al.  IR spectroscopy of aqueous alkali halide solutions: Pure salt-solvated water spectra and hydration numbers , 2001 .

[27]  A. Soper Determination of the orientational pair correlation function of a molecular liquid from diffraction data , 1998 .

[28]  M. Fontana,et al.  Raman spectroscopy and local order in aqueous solutions of strong II–I electrolytes , 1978 .

[29]  A. Fontana,et al.  Light and neutron scattering studies of the OH stretching band in liquid and supercritical water , 1998 .

[30]  R. Clark,et al.  Advances in Infrared and Raman Spectroscopy , 1982 .

[31]  A. Soper,et al.  Structure of 2 molar NaOH in aqueous solution from neutron diffraction and empirical potential structure refinement , 2006 .

[32]  M. Tuckerman,et al.  Ab Initio Molecular Dynamics Investigation of the Concentration Dependence of Charged Defect Transport in Basic Solutions via Calculation of the Infrared Spectrum , 2002 .

[33]  Bin Chen,et al.  Solvation structure and mobility mechanism of OH-: A car-parrinello molecular dynamics investigation of alkaline solutions , 2002 .

[34]  M. Nardone,et al.  Structural properties of disordered aqueous systems: a raman spectral investigation , 1976 .

[35]  R. Pecora Dynamic Light Scattering , 1985 .

[36]  Qiang Sun,et al.  Raman spectroscopic studies of the stretching band from water up to 6 kbar at 290 K , 2003 .

[37]  A. Faraone,et al.  Evidence of the existence of the low-density liquid phase in supercooled, confined water , 2007, Proceedings of the National Academy of Sciences.

[38]  Alan K. Soper,et al.  Empirical potential Monte Carlo simulation of fluid structure , 1996 .

[39]  M. Parrinello,et al.  The nature and transport mechanism of hydrated hydroxide ions in aqueous solution , 2002, Nature.

[40]  M. Parrinello,et al.  The nature of the hydrated excess proton in water , 1999, Nature.

[41]  A. Soper Partial structure factors from disordered materials diffraction data: An approach using empirical potential structure refinement , 2005 .