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Title: Development of a ReaxFF Potential for Carbon Condensed Phases and Its Application to the Thermal Fragmentation of a Large Fullerene

Abstract

In this article, we report the development of a ReaxFF reactive potential that can accurately describe the chemistry and dynamics of carbon condensed phases. Density functional theory (DFT)-based calculations were performed to obtain the equation of state for graphite and diamond and the formation energies of defects in graphene and amorphous phases from fullerenes. The DFT data were used to reparametrize ReaxFFCHO, resulting in a new potential called ReaxFFC-2013. ReaxFFC-2013 accurately predicts the atomization energy of graphite and closely reproduces the DFT-based energy difference between graphite and diamond, and the barrier for transition from graphite to diamond. ReaxFFC-2013 also accurately predicts the DFT-based energy barrier for Stone–Wales transformation in a C60(Ih) fullerene through the concerted rotation of a C2 unit. Later, MD simulations of a C180 fullerene using ReaxFFC-2013 suggested that the thermal fragmentation of these giant fullerenes is an exponential function of time. An Arrhenius-type equation was fit to the decay rate, giving an activation energy of 7.66 eV for the loss of carbon atoms from the fullerene. Although the decay of the molecule occurs primarily via the loss of C2 units, we observed that, with an increase in temperature, the probability of loss of larger fragments increases. Themore » ReaxFFC-2013 potential developed in this work, and the results obtained on fullerene fragmentation, provide an important step toward the full computational chemical modeling of coal pyrolysis, soot incandescence, high temperature erosion of graphitic rocket nozzles, and ablation of carbon-based spacecraft materials during atmospheric reentry.« less

Authors:
 [1];  [1];  [2]
  1. Department of Mechanical and Nuclear Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
  2. Centre for Nanophase Materials Sciences, Oak Ridge National Laboratory, P.O. Box 2008, MS 6494, Oak Ridge, Tennessee 37831, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1386358
DOE Contract Number:  
ERKCC61
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory; Journal Volume: 119; Journal Issue: 4; Related Information: FIRST partners with Oak Ridge National Laboratory (lead); Argonne National Laboratory; Drexel University; Georgia State University; Northwestern University; Pennsylvania State University; Suffolk University; Vanderbilt University; University of Virginia
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; catalysis (heterogeneous), solar (fuels), energy storage (including batteries and capacitors), hydrogen and fuel cells, electrodes - solar, mechanical behavior, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Srinivasan, Sriram Goverapet, van Duin, Adri C. T., and Ganesh, P.. Development of a ReaxFF Potential for Carbon Condensed Phases and Its Application to the Thermal Fragmentation of a Large Fullerene. United States: N. p., 2015. Web. doi:10.1021/jp510274e.
Srinivasan, Sriram Goverapet, van Duin, Adri C. T., & Ganesh, P.. Development of a ReaxFF Potential for Carbon Condensed Phases and Its Application to the Thermal Fragmentation of a Large Fullerene. United States. doi:10.1021/jp510274e.
Srinivasan, Sriram Goverapet, van Duin, Adri C. T., and Ganesh, P.. Tue . "Development of a ReaxFF Potential for Carbon Condensed Phases and Its Application to the Thermal Fragmentation of a Large Fullerene". United States. doi:10.1021/jp510274e.
@article{osti_1386358,
title = {Development of a ReaxFF Potential for Carbon Condensed Phases and Its Application to the Thermal Fragmentation of a Large Fullerene},
author = {Srinivasan, Sriram Goverapet and van Duin, Adri C. T. and Ganesh, P.},
abstractNote = {In this article, we report the development of a ReaxFF reactive potential that can accurately describe the chemistry and dynamics of carbon condensed phases. Density functional theory (DFT)-based calculations were performed to obtain the equation of state for graphite and diamond and the formation energies of defects in graphene and amorphous phases from fullerenes. The DFT data were used to reparametrize ReaxFFCHO, resulting in a new potential called ReaxFFC-2013. ReaxFFC-2013 accurately predicts the atomization energy of graphite and closely reproduces the DFT-based energy difference between graphite and diamond, and the barrier for transition from graphite to diamond. ReaxFFC-2013 also accurately predicts the DFT-based energy barrier for Stone–Wales transformation in a C60(Ih) fullerene through the concerted rotation of a C2 unit. Later, MD simulations of a C180 fullerene using ReaxFFC-2013 suggested that the thermal fragmentation of these giant fullerenes is an exponential function of time. An Arrhenius-type equation was fit to the decay rate, giving an activation energy of 7.66 eV for the loss of carbon atoms from the fullerene. Although the decay of the molecule occurs primarily via the loss of C2 units, we observed that, with an increase in temperature, the probability of loss of larger fragments increases. The ReaxFFC-2013 potential developed in this work, and the results obtained on fullerene fragmentation, provide an important step toward the full computational chemical modeling of coal pyrolysis, soot incandescence, high temperature erosion of graphitic rocket nozzles, and ablation of carbon-based spacecraft materials during atmospheric reentry.},
doi = {10.1021/jp510274e},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 4,
volume = 119,
place = {United States},
year = {Tue Jan 20 00:00:00 EST 2015},
month = {Tue Jan 20 00:00:00 EST 2015}
}