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Title: Transferable density functional tight binding for carbon, hydrogen, nitrogen, and oxygen: Application to shock compression

A new parameterization for density functional tight binding (DFTB) theory, lanl31, has been developed for molecules containing carbon, hydrogen, nitrogen, and oxygen. Optimal values for the Hubbard Us, on-site energies, and the radial dependences of the bond integrals and repulsive potentials were determined by numerical optimization using simulated annealing to a modest database of ab initio-calculated atomization energies and interatomic forces. The transferability of the optimized DFTB parameterization has been assessed using the CHNO subset of the QM-9 database [R. Ramakrishnan et al., Sci. Data, 1, 140022 (2014)]. These analyses showed that the errors in the atomization energies and interatomic forces predicted by our model are small and in the vicinity of the di erences between density functional theory calculations with di erent basis sets and exchange-correlation functionals. Good correlations between the molecular dipole moments and HOMO-LUMO gaps predicted by lanl31 and the QM-9 data set are also found. Furthermore, the errors in the atomization energies and forces derived from lanl31 are signi cantly smaller than those obtained from the ReaxFF-lg reactive force eld for organic materials [L. Liu et al., J. Phys. Chem. A, 115, 11016 (2011)]. The lanl31 DFTB parameterization for C, H, N, and O has beenmore » applied the to the molecular dynamics simulation of the principal Hugoniot of liquid nitromethane, liquid benzene, liquid nitrogen, pentaerythritol tetranitrate, trinitrotoluene, and cyclotetramethylene tetranitramine. The computed and measured Hugoniot loci are in excellent agreement with experiment and we discuss the sensitivity of the loci to the underestimated shock heating that is a characteristic of classical molecular dynamics simulations.« less
Authors:
ORCiD logo [1] ;  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Report Number(s):
LA-UR-18-29043
Journal ID: ISSN 0021-9606
Grant/Contract Number:
89233218CNA000001
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 2; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1492539

Cawkwell, M. J., and Perriot, R.. Transferable density functional tight binding for carbon, hydrogen, nitrogen, and oxygen: Application to shock compression. United States: N. p., Web. doi:10.1063/1.5063385.
Cawkwell, M. J., & Perriot, R.. Transferable density functional tight binding for carbon, hydrogen, nitrogen, and oxygen: Application to shock compression. United States. doi:10.1063/1.5063385.
Cawkwell, M. J., and Perriot, R.. 2019. "Transferable density functional tight binding for carbon, hydrogen, nitrogen, and oxygen: Application to shock compression". United States. doi:10.1063/1.5063385.
@article{osti_1492539,
title = {Transferable density functional tight binding for carbon, hydrogen, nitrogen, and oxygen: Application to shock compression},
author = {Cawkwell, M. J. and Perriot, R.},
abstractNote = {A new parameterization for density functional tight binding (DFTB) theory, lanl31, has been developed for molecules containing carbon, hydrogen, nitrogen, and oxygen. Optimal values for the Hubbard Us, on-site energies, and the radial dependences of the bond integrals and repulsive potentials were determined by numerical optimization using simulated annealing to a modest database of ab initio-calculated atomization energies and interatomic forces. The transferability of the optimized DFTB parameterization has been assessed using the CHNO subset of the QM-9 database [R. Ramakrishnan et al., Sci. Data, 1, 140022 (2014)]. These analyses showed that the errors in the atomization energies and interatomic forces predicted by our model are small and in the vicinity of the di erences between density functional theory calculations with di erent basis sets and exchange-correlation functionals. Good correlations between the molecular dipole moments and HOMO-LUMO gaps predicted by lanl31 and the QM-9 data set are also found. Furthermore, the errors in the atomization energies and forces derived from lanl31 are signi cantly smaller than those obtained from the ReaxFF-lg reactive force eld for organic materials [L. Liu et al., J. Phys. Chem. A, 115, 11016 (2011)]. The lanl31 DFTB parameterization for C, H, N, and O has been applied the to the molecular dynamics simulation of the principal Hugoniot of liquid nitromethane, liquid benzene, liquid nitrogen, pentaerythritol tetranitrate, trinitrotoluene, and cyclotetramethylene tetranitramine. The computed and measured Hugoniot loci are in excellent agreement with experiment and we discuss the sensitivity of the loci to the underestimated shock heating that is a characteristic of classical molecular dynamics simulations.},
doi = {10.1063/1.5063385},
journal = {Journal of Chemical Physics},
number = 2,
volume = 150,
place = {United States},
year = {2019},
month = {1}
}

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