A new molecular dynamics model in which the point charges on atomic sites are allowed to fluctuate in response to the environment is developed and applied to water. The idea for treating charges as variables is based on the concept of electronegativity equalization according to which: (a) the electronegativity of an atomic site is dependent on the atom’s type and charge and is perturbed by the electrostatic potential it experiences from its neighbors and (b) charge is transferred between atomic sites in such a way that electronegativities are equalized. The charges are treated as dynamical variables using an extended Lagrangian method in which the charges are given a fictitious mass, velocities, and kinetic energy and then propagated according to Newtonian mechanics along with the atomic degrees of freedom. Models for water with fluctuating charges are developed using the geometries of two common fixed‐charge water potentials: the simple point charge (SPC) and the four‐point transferable intermolecular po...

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Dynamical fluctuating charge force fields: Application to liquid water

Experimental permittivity data of liquid water, compiled from the open literature, were selectively applied to support a modeling strategy. Frequencies up to 1 THz and atmospheric temperatures are covered with an expression made up by two relaxation (Debye) terms. The double-Debye model reduces to one term when the high frequency limit is set at 100 GHz, and the model can be extended to 30 THz by adding two resonance (Lorentzian) terms. The scheme was carried out by employing nonlinear least-squares fitting routines to data we considered reliable.

A model for the complex permittivity of water at frequencies below 1 THz

The previously reported nonreproducibility of the intensity of the OH stretching band of liquid water has been explored. It was found that it can be eliminated in measurements with the Circle® multiple ATR cell by ensuring that the ATR rod is coaxial with the glass liquid holder. It was also found that normal laboratory temperature variations of a few degrees change the intensity by ≤~1% of the peak height. A new imaginary refractive index spectrum of water has been determined between 4000 and 700 cm-1 as the average of spectra calculated from ATR spectra recorded by four workers in our laboratory over the past seven years. It was obtained under experimental and computational conditions superior to those used previously, but is only marginally different from the spectra reported in 1989. In particular, the integrated intensities of the fundamentals are not changed significantly from those reported in 1989. The available imaginary refractive index, k, values between 15,000 and 1 cm-1 have been compared. The values that are judged to be the most reliable have been combined into a recommended k spectrum of H2O(l) at 25°C between 15,000 and 1 cm-1, from which the real refractive index spectrum has been calculated by Kramers-Kronig transformation. The recommended values of the real and imaginary refractive indices and molar absorption coefficients of liquid water at 25 ± 1 °C are presented in graphs and tables. The real and imaginary dielectric constants and the real and imaginary molar polarizabilities in this wavenumber range can be calculated from the tables. Conservatively estimated probable errors of the recommended k values are given. The precision with which the values can be measured in one laboratory and the relative errors between regions are, of course, far smaller than these probable errors. The recommended k values should be of considerable value as interim standard intensities of liquid water, which will facilitate the transfer of intensities between laboratories.

Infrared Intensities of Liquids XX: The Intensity of the OH Stretching Band of Liquid Water Revisited, and the Best Current Values of the Optical Constants of H 2 O(l) at 25°C between 15,000 and 1 cm -1

We report measurements of the real and imaginary part of the dielectric constant of liquid water in the far-infrared region from 0.1 to 2.0 THz in a temperature range from 271.1 to 366.7 K. The data have been obtained with the use of THz time domain reflection spectroscopy, utilizing ultrashort electromagnetic pulses generated from a photoconductive antenna driven by femtosecond laser pulses. A Debye model with an additional relaxation time is used to fit the frequency dependence of the complex dielectric constants. We obtain a fast (fs) and a Debye (ps) relaxation time for the macroscopic polarization. The corresponding time correlation functions have been calculated with molecular dynamics simulations and are compared with experimental relaxation times. The temperature dependence of the Debye relaxation time is analyzed using three models: Transition state theory, a Debye–Stoke–Einstein relation between the viscosity and the Debye time, and a model stating that its temperature dependence can be extrapolated from a singularity of liquid water at 228 K. We find an excellent agreement between experiment and the two latter models. The simulations, however, present results with too large statistical error for establishing a relation for the temperature dependence.

Investigation of the temperature dependence of dielectric relaxation in liquid water by thz reflection spectroscopy and molecular dynamics simulation

All the currently available experimental permittivity data for pure water are used to derive an interpolation function that precisely represents e(ν,t,) at standard atmospheric pressure, for frequencies and temperatures in the ranges 0⩽ν⩽25THz and 0⩽t⩽100°C. The permittivity data is represented in terms of relaxations and resonances processes. There are three relaxations in the microwave region and two resonances in the far infrared. The temperature dependence of the relaxation and resonance parameters are determined. For example, at 25°C the three relaxation frequencies are 18.56GHz, 167.83GHz, 1.944THz and the two resonance frequencies are 4.03 and 14.48THz.

Permittivity of pure water, at standard atmospheric pressure, over the frequency range 0-25 THz and the temperature range 0-100 °C

Various advances in technique have enabled new measurements to be made over a greatly extended frequency range (6<ν∼<450cm−1) of the optical constants n(ν∼) and α(ν∼) of liquid water and liquid D2O at 19°C. The origin of the polarization in this region is discussed.

M. N. Afsar

Papers

Measurements of the optical constants of liquid H 2 O and D 2 O between 6 and 450 cm −1