skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Final Report: Ionization chemistry of high temperature molecular fluids

Abstract

With the advent of coupled chemical/hydrodynamic reactive flow models for high explosives, understanding detonation chemistry is of increasing importance to DNT. The accuracy of first principles detonation codes, such as CHEETAH, are dependent on an accurate representation of the species present under detonation conditions. Ionic species and non-molecular phases are not currently included coupled chemistry/hydrodynamic simulations. This LDRD will determine the prevalence of such species during high explosive detonations, by carrying out experimental and computational investigation of common detonation products under extreme conditions. We are studying the phase diagram of detonation products such as H{sub 2}O, or NH{sub 3} and mixtures under conditions of extreme pressure (P > 1 GPa) and temperature (T > 1000K). Under these conditions, the neutral molecular form of matter transforms to a phase dominated by ions. The phase boundaries of such a region are unknown.

Authors:
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
902316
Report Number(s):
UCRL-TR-228525
TRN: US200717%%537
DOE Contract Number:
W-7405-ENG-48
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; CHEMICAL EXPLOSIVES; CHEMISTRY; EXPLOSIONS; FLOW MODELS; IONIZATION; MIXTURES; PHASE DIAGRAMS

Citation Formats

Fried, L E. Final Report: Ionization chemistry of high temperature molecular fluids. United States: N. p., 2007. Web. doi:10.2172/902316.
Fried, L E. Final Report: Ionization chemistry of high temperature molecular fluids. United States. doi:10.2172/902316.
Fried, L E. Mon . "Final Report: Ionization chemistry of high temperature molecular fluids". United States. doi:10.2172/902316. https://www.osti.gov/servlets/purl/902316.
@article{osti_902316,
title = {Final Report: Ionization chemistry of high temperature molecular fluids},
author = {Fried, L E},
abstractNote = {With the advent of coupled chemical/hydrodynamic reactive flow models for high explosives, understanding detonation chemistry is of increasing importance to DNT. The accuracy of first principles detonation codes, such as CHEETAH, are dependent on an accurate representation of the species present under detonation conditions. Ionic species and non-molecular phases are not currently included coupled chemistry/hydrodynamic simulations. This LDRD will determine the prevalence of such species during high explosive detonations, by carrying out experimental and computational investigation of common detonation products under extreme conditions. We are studying the phase diagram of detonation products such as H{sub 2}O, or NH{sub 3} and mixtures under conditions of extreme pressure (P > 1 GPa) and temperature (T > 1000K). Under these conditions, the neutral molecular form of matter transforms to a phase dominated by ions. The phase boundaries of such a region are unknown.},
doi = {10.2172/902316},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Mon Feb 26 00:00:00 EST 2007},
month = {Mon Feb 26 00:00:00 EST 2007}
}

Technical Report:

Save / Share:
  • The main thrust of this work was directed to the task of determining the thermodynamic behavior of condensed solids and fluids containing simple molecules. Properties calculated include specific heats, equations of state, compressibilities, sound velocities, virial coefficients, viscosities, and thermal expansion. In addition, details of the structural, orientational, and magnetic phase transitions were determined. Dynamical quantities calculated include the lattice, libron, and vibron mode frequencies at various pressures and temperatures. Also, we developed new techniques required to meet our objectives. One was a method for accurately calculating the Gibbs free energy of various phases. Another is the multiple-histogram Monte Carlomore » which can dramatically reduce computing time and can provide a continuous map of thermodynamic averages over a range of some thermodynamical variable.« less
  • Accomplishments during the grant period are presented. These lines of study were pursued: a benchmark study of the Jahn-Teller effect in benzene cation; the PIRI spectra of phenylacetylene and benzonitrile; a new approach to the calculation of vibronic coupling; anomalous line broadening in high resolution spectra; and long-lived species and anomalous photophysics in phenylacetylene;
  • Equilibrium structures, orientations, and magnetic order, lattice librational and vibrational mode frequencies, intramolecular vibron mode frequencies, sound velocities, equations of state, compressibilities, thermal expansion coefficients, and phase transitions in molecular solids over a wide range of temperatures and were pressures were determined. Except for structures and orientations, which are not static, similar properties were calculated in the fluid, in addition to virial coefficients, viscosities, specific heats, and dyamic correlations of positions, orientation, and local magnetic order. Techniques used include several strategies to optimize multi-dimensional functions as a means to determine structures and orientations, as does constant pressure and constant volume.more » Monte Carlo methods which also yields thermodynamic quantities and is a powerful method for characterizing phase transitions. Lattice dynamics, mean field methods, and classical perturbation theory are some of the analytic tools we use to determine dynamical features. Systems studied include H/sub 2/, N/sub 2/, O/sub 2/, CO, CO/sub 2/, F/sub 2/, I/sub 2/, N/sub 2/O, Cl/sub 2/, Br/sub 2/, HCl, HBr, and HI. 30 refs.« less
  • The objective is to determine the equilibrium structures and orientations, lattice vibrational and librational mode frequencies, intramolecular vibron mode frequencies, sound velocities, equations of state, compressibilities, and structural and orientational phase transitions in molecular solids over a wide range of pressures and temperatures. In the high temperature fluid phase the equations of state, vibron frequencies, and melting transition, specific heats, compressibilities, second virial coefficients, viscosities and other transport properties, and the nature of orientational and magnetic correlations will be determined. The techniques used include several strategies to optimize multi-dimensional function as a means to determine equilibrium structures and orientations, self-consistentmore » phonon lattice dynamics methods, constant pressure and constant volume Monte-Carlo strategies with continuously deformable boundary conditions, mean field approximations, and classical perturbation methods. Systems to be studied include H/sub 2/, N/sub 2/, O/sub 2/, CO, CO/sub 2/, F/sub 2/, N/sub 2/O, benzine, HCL, HBr, and Cl/sub 2/. 40 refs.« less
  • Equilibrium structures and orientations, lattice vibrational and librational model frequencies, intramolecular vibron mode frequencies, sound velocities, equations of state, compressibilities, and structural and orientational phase transitions in molecular solids are determined over a wide range of pressures and temperatures. In the high temperature fluid phase the equations of state, vibron frequencies, the melting transition, specific heats, compressibilities, second virial coefficients, viscosities and other transport properties, and the nature of orientational and magnetic correlations are determined. The techniques used include several strategies to optimize multi-dimensional functions as a means to determine equilibrium structures and orientations, self consistent phonon lattice dynamics methods,more » constant pressure and constant volume Monte-Carlo strategies with continuously deformable boundary conditions, mean field approximations, and classical perturbation methods. Systems studied include N/sub 2/, O/sub 2/, CO, CO/sub 2/, F/sub 2/, N/sub 2/O, benzine, nitromethane, HCL, HBr, and H/sub 2/. 50 refs., 4 figs.« less