Reactive Molecular Dynamics Simulations and Quantum Chemistry Calculations To Investigate Soot-Relevant Reaction Pathways for Hexylamine Isomers

Kwon, Hyunguk; Etz, Brian D.; Montgomery, Matthew J.; Messerly, Richard; Shabnam, Sharmin; Vyas, Shubham; van Duin, Adri C.  T.; McEnally, Charles S.; Pfefferle, Lisa D.; Kim, Seonah; Xuan, Yuan

doi:10.1021/acs.jpca.0c03355

Reactive Molecular Dynamics Simulations and Quantum Chemistry Calculations To Investigate Soot-Relevant Reaction Pathways for Hexylamine Isomers

Journal Article · Mon May 04 00:00:00 EDT 2020 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.0c03355· OSTI ID:1630117

^[1]; Etz, Brian D. ^[2]; ^[3]; Messerly, Richard ^[4]; Shabnam, Sharmin ^[5]; ^[6]; ^[5]; ^[3]; Pfefferle, Lisa D. ^[3]; ^[4]; Xuan, Yuan ^[5]

Pennsylvania State Univ., University Park, PA (United States); Yale University
National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
Yale Univ., New Haven, CT (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Pennsylvania State Univ., University Park, PA (United States)
Colorado School of Mines, Golden, CO (United States)

Sooting tendencies of a series of nitrogen-containing hydrocarbons (NHCs) have been recently characterized experimentally using the yield sooting index (YSI) methodology. In this work, we aim to identify soot-relevant reaction pathways for three selected C₆H₁₅N amines, namely, dipropylamine (DPA), di-isopropylamine (DIPA), and 3,3-dimethylbutylamine (DMBA) using ReaxFF molecular dynamics (MD) simulations and quantum mechanical (QM) calculations and to interpret the experimentally observed trends. ReaxFF MD simulations are performed to determine the important intermediate species and radicals involved in the fuel decomposition and soot formation processes. QM calculations are employed to extensively search for chemical reactions involving these species and radicals based on the ReaxFF MD results and also to quantitatively characterize the potential energy surfaces. Specifically, ReaxFF simulations are carried out in the NVT ensemble at 1400, 1600, and 1800 K, where soot has been identified to form in the YSI experiment. These simulations account for the interactions among test fuel molecules and pre-existing radicals and intermediate species generated from rich methane combustion, using a recently proposed simulation framework. ReaxFF simulations predict that the reactivity of the amines decrease in the order of DIPA > DMBA > DPA, independent of temperature. Both QM calculations and ReaxFF simulations predict that C₂H₄, C₃H₆, and C₄H₈ are the main non-aromatic soot precursors formed during the decomposition of DPA, DIPA, and DMBA, respectively, and the associated reaction pathways are identified for each amine. Both theoretical methods predict that sooting tendency increases in the order of DPA, DIPA, and DMBA, consistent with the experimentally measured trend in YSI. This work demonstrates that sooting tendencies and soot-relevant reaction pathways of fuels with unknown chemical kinetics can be identified efficiently through combined ReaxFF and QM simulations. Overall, predictions from ReaxFF simulations and QM calculations are consistent, in terms of fuel reactivity, major intermediates, and major non-aromatic soot precursors.

View Accepted Manuscript (DOE)

Research Organization:: Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Science Foundation (NSF); Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: EE0007983; AC36-99GO10337

OSTI ID:: 1630117

Alternate ID(s):: OSTI ID: 1660005

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 21 Vol. 124; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Computational Chemistry Young, David C. John Wiley & Sons, Inc. https://doi.org/10.1002/0471220655	book	January 2001
Biofuel Combustion Chemistry: From Ethanol to Biodiesel Kohse-Höinghaus, Katharina; Oßwald, Patrick; Cool, Terrill A. Angewandte Chemie International Edition, Vol. 49, Issue 21 https://doi.org/10.1002/anie.200905335	journal	May 2010
Advanced Biofuels and Beyond: Chemistry Solutions for Propulsion and Production Leitner, Walter; Klankermayer, Jürgen; Pischinger, Stefan Angewandte Chemie International Edition, Vol. 56, Issue 20 https://doi.org/10.1002/anie.201607257	journal	April 2017
Supramolecular Binding Thermodynamics by Dispersion-Corrected Density Functional Theory Grimme, Stefan Chemistry - A European Journal, Vol. 18, Issue 32 https://doi.org/10.1002/chem.201200497	journal	July 2012
Shock Tube Study of Dimethylamine Oxidation: SHOCK TUBE STUDY OF DIMETHYLAMINE OXIDATION Li, Sijie; Davidson, David F.; Hanson, Ronald K. International Journal of Chemical Kinetics, Vol. 47, Issue 1 https://doi.org/10.1002/kin.20888	journal	November 2014
Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom: AUTOMATED REACTION MECHANISM GENERATION INCLUDING NITROGEN AS A HETEROATOM Dana, Alon Grinberg; Buesser, Beat; Merchant, Shamel S. International Journal of Chemical Kinetics, Vol. 50, Issue 4 https://doi.org/10.1002/kin.21154	journal	February 2018
Experimental study of fuel decomposition and hydrocarbon growth processes for practical fuel components: heptanes McEnally, Charles S.; Ciuparu, Dragos M.; Pfefferle, Lisa D. Combustion and Flame, Vol. 134, Issue 4 https://doi.org/10.1016/S0010-2180(03)00113-5	journal	September 2003
Kinetics of the thermal decomposition of the n-propyl radical Bencsura, Ákos; Knyazev, Vadim D.; Xing, Shi-Ben Symposium (International) on Combustion, Vol. 24, Issue 1 https://doi.org/10.1016/S0082-0784(06)80077-9	journal	January 1992
The influence of gaseous additives on the formation of soot in premixed flames Haynes, B. S.; Jander, H.; Mätzing, H. Symposium (International) on Combustion, Vol. 19, Issue 1 https://doi.org/10.1016/S0082-0784(82)80314-7	journal	January 1982
Fuel-nitrogen conversion in the combustion of small amines using dimethylamine and ethylamine as biomass-related model fuels Lucassen, Arnas; Zhang, Kuiwen; Warkentin, Julia Combustion and Flame, Vol. 159, Issue 7 https://doi.org/10.1016/j.combustflame.2012.02.024	journal	July 2012
Numerical modeling of sooting tendencies in a laminar co-flow diffusion flame Xuan, Yuan; Blanquart, Guillaume Combustion and Flame, Vol. 160, Issue 9 https://doi.org/10.1016/j.combustflame.2013.03.034	journal	September 2013
Measuring and predicting sooting tendencies of oxygenates, alkanes, alkenes, cycloalkanes, and aromatics on a unified scale Das, Dhrubajyoti D.; St. John, Peter C.; McEnally, Charles S. Combustion and Flame, Vol. 190 https://doi.org/10.1016/j.combustflame.2017.12.005	journal	April 2018
A comparative study on the sooting tendencies of various 1-alkene fuels in counterflow diffusion flames Wang, Yu; Park, Sungwoo; Sarathy, S. Mani Combustion and Flame, Vol. 192 https://doi.org/10.1016/j.combustflame.2018.01.033	journal	June 2018
Assessment of Gaussian-4 theory for energy barriers Curtiss, Larry A.; Redfern, Paul C.; Raghavachari, Krishnan Chemical Physics Letters, Vol. 499, Issue 1-3 https://doi.org/10.1016/j.cplett.2010.09.012	journal	October 2010
Pyrolysis of binary fuel mixtures at supercritical conditions: A ReaxFF molecular dynamics study Ashraf, Chowdhury; Shabnam, Sharmin; Jain, Abhishek Fuel, Vol. 235 https://doi.org/10.1016/j.fuel.2018.07.077	journal	January 2019
Numerical investigation of the pressure-dependence of yield sooting indices for n-alkane and aromatic species Kwon, Hyunguk; Jain, Abhishek; McEnally, Charles S. Fuel, Vol. 254 https://doi.org/10.1016/j.fuel.2019.05.157	journal	October 2019
Numerical simulations of yield-based sooting tendencies of aromatic fuels using ReaxFF molecular dynamics Kwon, Hyunguk; Shabnam, Sharmin; van Duin, Adri C. T. Fuel, Vol. 262 https://doi.org/10.1016/j.fuel.2019.116545	journal	February 2020
Studies of aromatic hydrocarbon formation mechanisms in flames: Progress towards closing the fuel gap McEnally, Charles S.; Pfefferle, Lisa D.; Atakan, Burak Progress in Energy and Combustion Science, Vol. 32, Issue 3 https://doi.org/10.1016/j.pecs.2005.11.003	journal	January 2006
Biofuels (alcohols and biodiesel) applications as fuels for internal combustion engines Agarwal, Avinash Kumar Progress in Energy and Combustion Science, Vol. 33, Issue 3 https://doi.org/10.1016/j.pecs.2006.08.003	journal	June 2007
Modeling nitrogen chemistry in combustion Glarborg, Peter; Miller, James A.; Ruscic, Branko Progress in Energy and Combustion Science, Vol. 67 https://doi.org/10.1016/j.pecs.2018.01.002	journal	July 2018
Fuel decomposition and hydrocarbon growth processes for oxygenated hydrocarbons: butyl alcohols McEnally, Charles S.; Pfefferle, Lisa D. Proceedings of the Combustion Institute, Vol. 30, Issue 1 https://doi.org/10.1016/j.proci.2004.07.033	journal	January 2005
Study on combustion characteristics and PM emission of diesel engines using ester–ethanol–diesel blended fuels Chen, Hu; Shi-Jin, Shuai; Jian-Xin, Wang Proceedings of the Combustion Institute, Vol. 31, Issue 2 https://doi.org/10.1016/j.proci.2006.07.130	journal	January 2007
Biomass cofiring impacts on flame structure and emissions Damstedt, Bradley; Pederson, Jesper M.; Hansen, Dane Proceedings of the Combustion Institute, Vol. 31, Issue 2 https://doi.org/10.1016/j.proci.2006.07.155	journal	January 2007
Bio-diesel effects on combustion processes in an HSDI diesel engine using advanced injection strategies Fang, Tiegang; Lee, Chia-fon F. Proceedings of the Combustion Institute, Vol. 32, Issue 2 https://doi.org/10.1016/j.proci.2008.07.031	journal	January 2009
Experimental and kinetic modeling study of laminar coflow diffusion methane flames doped with iso-butanol Jin, Hanfeng; Wang, Guoqing; Wang, Yizun Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.06.111	journal	January 2017
Real-time observation of soot aggregate oxidation in an Environmental Transmission Electron Microscope Sediako, Anton D.; Soong, Charles; Howe, Jane Y. Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.07.048	journal	January 2017
Sooting tendencies of co-optima test gasolines and their surrogates McEnally, Charles S.; Xuan, Yuan; St. John, Peter C. Proceedings of the Combustion Institute, Vol. 37, Issue 1 https://doi.org/10.1016/j.proci.2018.05.071	journal	January 2019
Developing detailed chemical kinetic mechanisms for fuel combustion Curran, Henry J. Proceedings of the Combustion Institute, Vol. 37, Issue 1 https://doi.org/10.1016/j.proci.2018.06.054	journal	January 2019
Experimental and theoretical insight into the soot tendencies of the methylcyclohexene isomers Kim, Seonah; Fioroni, Gina M.; Park, Ji-Woong Proceedings of the Combustion Institute, Vol. 37, Issue 1 https://doi.org/10.1016/j.proci.2018.06.095	journal	January 2019
A Quantitative Model for the Prediction of Sooting Tendency from Molecular Structure St. John, Peter C.; Kairys, Paul; Das, Dhrubajyoti D. Energy & Fuels, Vol. 31, Issue 9 https://doi.org/10.1021/acs.energyfuels.7b00616	journal	August 2017
Theoretical Study of Mechanism and Dynamics on Reaction of (CH ₃ ) ₂ NH with CH ₃ Gong, Shida; Luo, Qiong; Wei, Gong Min The Journal of Physical Chemistry A, Vol. 119, Issue 20 https://doi.org/10.1021/acs.jpca.5b02443	journal	May 2015
Benchmarking Compound Methods (CBS-QB3, CBS-APNO, G3, G4, W1BD) against the Active Thermochemical Tables: Formation Enthalpies of Radicals Somers, Kieran P.; Simmie, John M. The Journal of Physical Chemistry A, Vol. 119, Issue 33 https://doi.org/10.1021/acs.jpca.5b05448	journal	August 2015
Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics Ashraf, Chowdhury; van Duin, Adri C. T. The Journal of Physical Chemistry A, Vol. 121, Issue 5 https://doi.org/10.1021/acs.jpca.6b12429	journal	January 2017
Atomistic Scale Analysis of the Carbonization Process for C/H/O/N-Based Polymers with the ReaxFF Reactive Force Field Kowalik, Malgorzata; Ashraf, Chowdhury; Damirchi, Behzad The Journal of Physical Chemistry B, Vol. 123, Issue 25 https://doi.org/10.1021/acs.jpcb.9b04298	journal	May 2019
Sooting Tendencies of Oxygenated Hydrocarbons in Laboratory-Scale Flames McEnally, Charles S.; Pfefferle, Lisa D. Environmental Science & Technology, Vol. 45, Issue 6 https://doi.org/10.1021/es103733q	journal	March 2011
Branching Ratios in Reactions of OH Radicals with Methylamine, Dimethylamine, and Ethylamine Onel, Lavinia; Blitz, Mark; Dryden, Matthew Environmental Science & Technology, Vol. 48, Issue 16 https://doi.org/10.1021/es502398r	journal	August 2014
Relation of Smoke Point to Molecular Structure Hunt, Russell A. Industrial & Engineering Chemistry, Vol. 45, Issue 3 https://doi.org/10.1021/ie50519a039	journal	March 1953
C−H Bond Dissociation Energies of Alkyl Amines: Radical Structures and Stabilization Energies ^§ Wayner, D. D. M.; Clark, K. B.; Rauk, A. Journal of the American Chemical Society, Vol. 119, Issue 38 https://doi.org/10.1021/ja971365v	journal	September 1997
ReaxFF: A Reactive Force Field for Hydrocarbons van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois The Journal of Physical Chemistry A, Vol. 105, Issue 41 https://doi.org/10.1021/jp004368u	journal	October 2001
A Shock Tube Study of OH + H ₂ O ₂ → H ₂ O + HO ₂ and H ₂ O ₂ + M → 2OH + M using Laser Absorption of H ₂ O and OH Hong, Zekai; Cook, Robert D.; Davidson, David F. The Journal of Physical Chemistry A, Vol. 114, Issue 18 https://doi.org/10.1021/jp100204z	journal	May 2010
Dissociation of Propyl Radicals and Other Reactions on a C ₃ H ₇ Potential Miller, James A.; Klippenstein, Stephen J. The Journal of Physical Chemistry A, Vol. 117, Issue 13 https://doi.org/10.1021/jp312712p	journal	February 2013
Benchmarking Compound Methods (CBS-QB3, CBS-APNO, G3, G4, W1BD) against the Active Thermochemical Tables: A Litmus Test for Cost-Effective Molecular Formation Enthalpies Simmie, John M.; Somers, Kieran P. The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/jp511403a	journal	January 2015
ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation Chenoweth, Kimberly; van Duin, Adri C. T.; Goddard, William A. The Journal of Physical Chemistry A, Vol. 112, Issue 5 https://doi.org/10.1021/jp709896w	journal	February 2008
The ReaxFF reactive force-field: development, applications and future directions Senftle, Thomas P.; Hong, Sungwook; Islam, Md Mahbubul npj Computational Materials, Vol. 2, Issue 1 https://doi.org/10.1038/npjcompumats.2015.11	journal	March 2016
An interatomic potential for saturated hydrocarbons based on the modified embedded-atom method Nouranian, S.; Tschopp, M. A.; Gwaltney, S. R. Phys. Chem. Chem. Phys., Vol. 16, Issue 13 https://doi.org/10.1039/C4CP00027G	journal	January 2014
Molecular understandings on the activation of light hydrocarbons over heterogeneous catalysts Zhao, Zhi-Jian; Chiu, Cheng-chau; Gong, Jinlong Chemical Science, Vol. 6, Issue 8 https://doi.org/10.1039/C5SC01227A	journal	January 2015
Global partitioning of NOx sources using satellite observations: Relative roles of fossil fuel combustion, biomass burning and soil emissions Jaeglé, Lyatt; Steinberger, Linda; Martin, Randall V. Faraday Discussions, Vol. 130 https://doi.org/10.1039/b502128f	journal	January 2005
Gaussian-4 theory Curtiss, Larry A.; Redfern, Paul C.; Raghavachari, Krishnan The Journal of Chemical Physics, Vol. 126, Issue 8 https://doi.org/10.1063/1.2436888	journal	February 2007
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
A second-generation reactive empirical bond order (REBO) potential energy expression for hydrocarbons Brenner, Donald W.; Shenderova, Olga A.; Harrison, Judith A. Journal of Physics: Condensed Matter, Vol. 14, Issue 4 https://doi.org/10.1088/0953-8984/14/4/312	journal	January 2002
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Empirical potential for hydrocarbons for use in simulating the chemical vapor deposition of diamond films Brenner, Donald W. Physical Review B, Vol. 42, Issue 15 https://doi.org/10.1103/PhysRevB.42.9458	journal	November 1990
Charge optimized many-body potential for the Si ∕ SiO 2 system Yu, Jianguo; Sinnott, Susan B.; Phillpot, Simon R. Physical Review B, Vol. 75, Issue 8 https://doi.org/10.1103/PhysRevB.75.085311	journal	February 2007
Second-generation charge-optimized many-body potential for Si / SiO 2 and amorphous silica Shan, Tzu-Ray; Devine, Bryce D.; Hawkins, Jeffery M. Physical Review B, Vol. 82, Issue 23 https://doi.org/10.1103/PhysRevB.82.235302	journal	December 2010

Similar Records

Reactive Molecular Dynamics Simulations and Quantum Chemistry Calculations To Investigate Soot-Relevant Reaction Pathways for Hexylamine Isomers

Journal Article · Mon May 04 00:00:00 EDT 2020 · Journal of Physical Chemistry A · OSTI ID:1660005

Numerical simulations of yield-based sooting tendencies of aromatic fuels using ReaxFF molecular dynamics

Journal Article · Thu Nov 07 23:00:00 EST 2019 · Fuel · OSTI ID:1574238

Pyrolysis of bio-derived dioxolane fuels: A ReaxFF molecular dynamics study

Journal Article · Wed Aug 11 00:00:00 EDT 2021 · Fuel · OSTI ID:1977133

Related Subjects

09 BIOMASS FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Reactive Molecular Dynamics Simulations and Quantum Chemistry Calculations To Investigate Soot-Relevant Reaction Pathways for Hexylamine Isomers

Citation Formats

References (54)

Similar Records

Related Subjects