Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Photofragmentation of Tetranitromethane: Spin-Unrestricted Time-Dependent Excited-State Molecular Dynamics

Abstract

In this study, the photofragmentation dynamics of tetranitromethane (TNM) is explored by a spin-unrestricted time-dependent excited-state molecular dynamics (u-TDESMD) algorithm based on Rabi oscillations and principles similar to trajectory surface hopping, with a midintensity field approximation. The leading order process is represented by the molecule undergoing cyclic excitations and de-excitations. During excitation cycles, the nuclear kinetic energy is accumulated to overcome the dissociation barriers in the reactant and a sequence of intermediates. The dissociation pathway includes the ejection of NO2 groups followed by the formation of NO and CO. The simulated mass spectra at the ab initio level, based on the bond length in possible fragments, are extracted from simulation trajectories. Finally, the recently developed methodology has the potential to model and monitor photoreactions with open-shell intermediates and radicals.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of South Dakota, Vermillion, SD (United States). Dept. of Chemistry; North Dakota State Univ., Fargo, ND (United States). Dept. of Chemistry and Biochemistry
  2. North Dakota State Univ., Fargo, ND (United States). Dept. of Coatings and Polymeric Materials
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1483859
Grant/Contract Number:  
AC02-05CH11231; SC0001717
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 14; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Han, Yulun, Rasulev, Bakhtiyor, and Kilin, Dmitri S. Photofragmentation of Tetranitromethane: Spin-Unrestricted Time-Dependent Excited-State Molecular Dynamics. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b01330.
Copy to clipboard
Han, Yulun, Rasulev, Bakhtiyor, & Kilin, Dmitri S. Photofragmentation of Tetranitromethane: Spin-Unrestricted Time-Dependent Excited-State Molecular Dynamics. United States. https://doi.org/10.1021/acs.jpclett.7b01330
Copy to clipboard
Han, Yulun, Rasulev, Bakhtiyor, and Kilin, Dmitri S. Fri . "Photofragmentation of Tetranitromethane: Spin-Unrestricted Time-Dependent Excited-State Molecular Dynamics". United States. https://doi.org/10.1021/acs.jpclett.7b01330. https://www.osti.gov/servlets/purl/1483859.
Copy to clipboard
@article{osti_1483859,
title = {Photofragmentation of Tetranitromethane: Spin-Unrestricted Time-Dependent Excited-State Molecular Dynamics},
author = {Han, Yulun and Rasulev, Bakhtiyor and Kilin, Dmitri S.},
abstractNote = {In this study, the photofragmentation dynamics of tetranitromethane (TNM) is explored by a spin-unrestricted time-dependent excited-state molecular dynamics (u-TDESMD) algorithm based on Rabi oscillations and principles similar to trajectory surface hopping, with a midintensity field approximation. The leading order process is represented by the molecule undergoing cyclic excitations and de-excitations. During excitation cycles, the nuclear kinetic energy is accumulated to overcome the dissociation barriers in the reactant and a sequence of intermediates. The dissociation pathway includes the ejection of NO2 groups followed by the formation of NO and CO. The simulated mass spectra at the ab initio level, based on the bond length in possible fragments, are extracted from simulation trajectories. Finally, the recently developed methodology has the potential to model and monitor photoreactions with open-shell intermediates and radicals.},
doi = {10.1021/acs.jpclett.7b01330},
journal = {Journal of Physical Chemistry Letters},
number = 14,
volume = 8,
place = {United States},
year = {Fri Jun 16 00:00:00 EDT 2017},
month = {Fri Jun 16 00:00:00 EDT 2017}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.7b01330
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Tetranitromethane as Oxidizer in Rocket Propellants
journal, April 1956

  • Tschinkel, Johann G.
  • Industrial & Engineering Chemistry, Vol. 48, Issue 4
  • DOI: 10.1021/ie50556a022

The Chemistry of Tetranitromethane
journal, November 1976

Electron Paramagnetic Resonance Study of the Photolysis of Nitromethane, Methyl Nitrite, and Tetranitromethane at 77°K. 1
journal, February 1964

  • Bielski, Benon H. J.; Timmons, Richard B.
  • The Journal of Physical Chemistry, Vol. 68, Issue 2
  • DOI: 10.1021/j100784a024

Tetranitromethane
journal, October 1949

  • Hager, Karl F.
  • Industrial & Engineering Chemistry, Vol. 41, Issue 10
  • DOI: 10.1021/ie50478a028

Protein Tyrosine Nitration: Selectivity, Physicochemical and Biological Consequences, Denitration, and Proteomics Methods for the Identification of Tyrosine-Nitrated Proteins
journal, June 2009

  • Abello, Nicolas; Kerstjens, Huib A. M.; Postma, Dirkje S.
  • Journal of Proteome Research, Vol. 8, Issue 7
  • DOI: 10.1021/pr900039c

Tetranitromethane. A Reagent for the Nitration of Tyrosyl Residues in Proteins *
journal, November 1966

  • Sokolovsky, Mordechai; Riordan, James F.; Vallee, Bert L.
  • Biochemistry, Vol. 5, Issue 11
  • DOI: 10.1021/bi00875a029

The explosive reaction of tetranitromethane with ferrocene
journal, June 1979

  • Jaworska-Augustyniak, Anna; Wojtczak, Jan
  • Transition Metal Chemistry, Vol. 4, Issue 3
  • DOI: 10.1007/BF00619069

The Pyrolysis of Tetranitromethane in the Gas Phase
journal, July 1992

  • Bock, Hans; Zanathy, L�szl�
  • Angewandte Chemie International Edition in English, Vol. 31, Issue 7
  • DOI: 10.1002/anie.199209001

The 347.2 nm Laser Photolysis of Tetranitromethane in Polar, Nonpolar, and Micellar Solutions
journal, July 1976

  • Frank, A. J.; Grätzel, M.; Henglein, A.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 80, Issue 7
  • DOI: 10.1002/bbpc.19760800705

Pulse radiolysis studies of solutions of tetranitromethane in iso-propanol
journal, January 1971

  • Asmus, K. -D.; Chaudhri, Shamim A.; Nazhat, N. B.
  • Transactions of the Faraday Society, Vol. 67
  • DOI: 10.1039/tf9716702607

Exploding Nitromethane in Silico, in Real Time
journal, September 2014

  • Fileti, Eudes Eterno; Chaban, Vitaly V.; Prezhdo, Oleg V.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 19
  • DOI: 10.1021/jz501848e

Ultrafast Photodissociation Dynamics of Nitromethane
journal, January 2016

  • Nelson, Tammie; Bjorgaard, Josiah; Greenfield, Margo
  • The Journal of Physical Chemistry A, Vol. 120, Issue 4
  • DOI: 10.1021/acs.jpca.5b09776

Transferable Reactive Force Fields: Extensions of ReaxFF- lg to Nitromethane
journal, February 2017

  • Larentzos, James P.; Rice, Betsy M.
  • The Journal of Physical Chemistry A, Vol. 121, Issue 9
  • DOI: 10.1021/acs.jpca.6b11761

Explosion Study of Nitromethane Confined in Carbon Nanotube Nanocontainer via Reactive Molecular Dynamics
journal, March 2017

  • Lee, Jeong Hyeon; Kim, Jin Chul; Jeon, Woo Cheol
  • The Journal of Physical Chemistry C, Vol. 121, Issue 12
  • DOI: 10.1021/acs.jpcc.6b11757

Nitromethane Decomposition under High Static Pressure
journal, July 2010

  • Citroni, Margherita; Bini, Roberto; Pagliai, Marco
  • The Journal of Physical Chemistry B, Vol. 114, Issue 29
  • DOI: 10.1021/jp1035508

Photoconductivities from band states and a dissipative electron dynamics: Si(111) without and with adsorbed Ag clusters
journal, January 2016

  • Vazhappilly, Tijo; Hembree, Robert H.; Micha, David A.
  • The Journal of Chemical Physics, Vol. 144, Issue 2
  • DOI: 10.1063/1.4938560

Dynamics of charge transfer at Au/Si metal-semiconductor nano-interface
journal, October 2013

Ab initio study of the photocurrent at the Au/Si metal–semiconductor nanointerface
journal, August 2014

How Shaped Light Discriminates Nearly Identical Biochromophores
journal, August 2010

GPU-Accelerated State-Averaged Complete Active Space Self-Consistent Field Interfaced with Ab Initio Multiple Spawning Unravels the Photodynamics of Provitamin D 3
journal, June 2016

  • Snyder, James W.; Curchod, Basile F. E.; Martínez, Todd J.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 13
  • DOI: 10.1021/acs.jpclett.6b00970

Unveiling the Role of Hot Charge-Transfer States in Molecular Aggregates via Nonadiabatic Dynamics
journal, March 2016

  • Fazzi, Daniele; Barbatti, Mario; Thiel, Walter
  • Journal of the American Chemical Society, Vol. 138, Issue 13
  • DOI: 10.1021/jacs.5b13210

Nonradiative Relaxation in Real-Time Electronic Dynamics OSCF2: Organolead Triiodide Perovskite
journal, August 2016

  • Nguyen, Triet S.; Parkhill, John
  • The Journal of Physical Chemistry A, Vol. 120, Issue 34
  • DOI: 10.1021/acs.jpca.6b06937

Mechanism of photocatalytic water oxidation on small TiO 2 nanoparticles
journal, January 2017

  • Muuronen, Mikko; Parker, Shane M.; Berardo, Enrico
  • Chemical Science, Vol. 8, Issue 3
  • DOI: 10.1039/C6SC04378J

Photoactive High Explosives: Linear and Nonlinear Photochemistry of Petrin Tetrazine Chloride
journal, May 2015

  • Greenfield, Margo T.; McGrane, Shawn D.; Bolme, Cindy A.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 20
  • DOI: 10.1021/acs.jpca.5b02092

Laser-Induced Explosion of Nitrated Carbon Nanotubes: Nonadiabatic and Reactive Molecular Dynamics Simulations
journal, December 2016

  • Chaban, Vitaly V.; Pal, Sougata; Prezhdo, Oleg V.
  • Journal of the American Chemical Society, Vol. 138, Issue 49
  • DOI: 10.1021/jacs.6b08082

Nonadiabatic excited-state molecular dynamics: On-the-fly limiting of essential excited states
journal, December 2016

First-Principles Study of Nonradiative Recombination in Silicon Nanocrystals: The Role of Surface Silanol
journal, September 2016

That Little Extra Kick: Nonadiabatic Effects in Acetaldehyde Photodissociation
journal, October 2016

  • Vincent, Jordan C.; Muuronen, Mikko; Pearce, Kirk C.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 20
  • DOI: 10.1021/acs.jpclett.6b02037

Ab initio Ehrenfest dynamics
journal, August 2005

  • Li, Xiaosong; Tully, John C.; Schlegel, H. Bernhard
  • The Journal of Chemical Physics, Vol. 123, Issue 8
  • DOI: 10.1063/1.2008258

Surface Structure and Silicon Nanocrystal Photoluminescence: The Role of Hypervalent Silyl Groups
journal, November 2015

  • Shu, Yinan; Kortshagen, Uwe R.; Levine, Benjamin G.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 47
  • DOI: 10.1021/acs.jpcc.5b08578

Photofragmentation of Gas-Phase Lanthanide Cyclopentadienyl Complexes: Experimental and Time-Dependent Excited-State Molecular Dynamics
journal, March 2014

  • Chen, Jiangchao; Hochstatter, Andrew M.; Kilin, Dmitri
  • Organometallics, Vol. 33, Issue 7
  • DOI: 10.1021/om400953q

Photofragmentation Pathways for Gas-Phase Lanthanide Tris(isopropylcyclopentadienyl) Complexes
journal, October 2016

Photofragmentation of the Gas-Phase Lanthanum Isopropylcyclopentadienyl Complex: Computational Modeling vs Experiment
journal, October 2015

  • Han, Yulun; Meng, Qingguo; Rasulev, Bakhtiyor
  • The Journal of Physical Chemistry A, Vol. 119, Issue 44
  • DOI: 10.1021/acs.jpca.5b07209

Electronic Structure and Bonding of {Fe(PhNO 2 )} 6 Complexes:  A Density Functional Theory Study
journal, May 2007

  • Isayev, Olexandr; Gorb, Leonid; Zilberberg, Igor
  • The Journal of Physical Chemistry A, Vol. 111, Issue 18
  • DOI: 10.1021/jp0668798

Spin Unrestricted Excited State Relaxation Study of Vanadium(IV)-Doped Anatase
journal, March 2016

  • Jensen, Stephanie J.; Inerbaev, Talgat M.; Kilin, Dmitri S.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 11
  • DOI: 10.1021/acs.jpcc.5b12167

Radical damage in lipids investigated with the fragment molecular orbital method
journal, May 2016

Efficient Molecular Dynamics Simulations of Multiple Radical Center Systems Based on the Fragment Molecular Orbital Method
journal, October 2014

  • Nakata, Hiroya; Schmidt, Michael W.; Fedorov, Dmitri G.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 41
  • DOI: 10.1021/jp507726m

Importance of Three-Body Interactions in Molecular Dynamics Simulations of Water Demonstrated with the Fragment Molecular Orbital Method
journal, March 2016

  • Pruitt, Spencer R.; Nakata, Hiroya; Nagata, Takeshi
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 4
  • DOI: 10.1021/acs.jctc.5b01208

Towards First Principles Calculation of Electron Impact Mass Spectra of Molecules
journal, April 2013

How to Compute Electron Ionization Mass Spectra from First Principles
journal, May 2016

  • Bauer, Christoph Alexander; Grimme, Stefan
  • The Journal of Physical Chemistry A, Vol. 120, Issue 21
  • DOI: 10.1021/acs.jpca.6b02907

Photoexcitation, Ionization, and Dissociation of Molecules Using Intense Near-Infrared Radiation of Femtosecond Duration
journal, August 1999

  • Levis, Robert J.; DeWitt, Merrick J.
  • The Journal of Physical Chemistry A, Vol. 103, Issue 33
  • DOI: 10.1021/jp984543v

Behavior of Polyatomic Molecules in Intense Infrared Laser Beams
journal, April 1998

  • Ledingham, K. W. D.; Singhal, R. P.; Smith, D. J.
  • The Journal of Physical Chemistry A, Vol. 102, Issue 18
  • DOI: 10.1021/jp9816162

Laser induced photodissociation of CH2Cl2 and CH2Br2 at 355 nm: an experimental and theoretical study
journal, December 2003

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965

Use of Rotating Coordinates in Magnetic Resonance Problems
journal, April 1954

Space Quantization in a Gyrating Magnetic Field
journal, April 1937

Dissipative Quantum Dynamics with Many Coupled Molecular States:  Photodesorption from Metal Surfaces
journal, August 2003

  • Micha, D. A.; Santana, A.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 37
  • DOI: 10.1021/jp030441f

Light-Driven and Phonon-Assisted Dynamics in Organic and Semiconductor Nanostructures
journal, May 2015

Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer in a Solvated Phenol–Amine Complex
journal, August 2014

  • Goyal, Puja; Schwerdtfeger, Christine A.; Soudackov, Alexander V.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 6
  • DOI: 10.1021/jp5126969

Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer: Comparison of Explicit and Implicit Solvent Simulations
journal, June 2012

  • Auer, Benjamin; Soudackov, Alexander V.; Hammes-Schiffer, Sharon
  • The Journal of Physical Chemistry B, Vol. 116, Issue 26
  • DOI: 10.1021/jp3031682

Proton transfer in solution: Molecular dynamics with quantum transitions
journal, September 1994

  • Hammes‐Schiffer, Sharon; Tully, John C.
  • The Journal of Chemical Physics, Vol. 101, Issue 6
  • DOI: 10.1063/1.467455

Open Babel: An open chemical toolbox
journal, October 2011

  • O'Boyle, Noel M.; Banck, Michael; James, Craig A.
  • Journal of Cheminformatics, Vol. 3, Issue 1
  • DOI: 10.1186/1758-2946-3-33

Sequential hydrogen dissociation from a charged Pt 13 H 24 cluster modeled by ab initio molecular dynamics
journal, August 2012

  • Meng, Qingguo; May, P. Stanley; Berry, Mary T.
  • International Journal of Quantum Chemistry, Vol. 112, Issue 24
  • DOI: 10.1002/qua.24301

Mathematical modeling of gas desorption from a metal–organic supercontainer cavity filled with stored N 2 gas at critical limits
journal, January 2017

  • Sapp, Wendi; Gifford, Brendan; Wang, Zhenqiang
  • RSC Advances, Vol. 7, Issue 18
  • DOI: 10.1039/C6RA21876H

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Inhomogeneous Electron Gas
journal, November 1964

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Buckybomb: Reactive Molecular Dynamics Simulation
journal, February 2015

  • Chaban, Vitaly V.; Fileti, Eudes Eterno; Prezhdo, Oleg V.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 5
  • DOI: 10.1021/acs.jpclett.5b00120

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 124, Issue 21
  • DOI: 10.1063/1.2204597

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

NIST Chemistry WebBook, NIST Standard Reference Database 69
dataset, January 1997

  • Linstrom, Peter
  • National Institute of Standards and Technology
  • DOI: 10.18434/T4D303

Transferable Reactive Force Fields: Extensions of ReaxFF- lg to Nitromethane
journal, February 2017

  • Larentzos, James P.; Rice, Betsy M.
  • The Journal of Physical Chemistry A, Vol. 121, Issue 9
  • DOI: 10.1021/acs.jpca.6b11761

GPU-Accelerated State-Averaged Complete Active Space Self-Consistent Field Interfaced with Ab Initio Multiple Spawning Unravels the Photodynamics of Provitamin D 3
journal, June 2016

  • Snyder, James W.; Curchod, Basile F. E.; Martínez, Todd J.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 13
  • DOI: 10.1021/acs.jpclett.6b00970

Laser-Induced Explosion of Nitrated Carbon Nanotubes: Nonadiabatic and Reactive Molecular Dynamics Simulations
journal, December 2016

  • Chaban, Vitaly V.; Pal, Sougata; Prezhdo, Oleg V.
  • Journal of the American Chemical Society, Vol. 138, Issue 49
  • DOI: 10.1021/jacs.6b08082

Electronic Structure and Bonding of {Fe(PhNO 2 )} 6 Complexes:  A Density Functional Theory Study
journal, May 2007

  • Isayev, Olexandr; Gorb, Leonid; Zilberberg, Igor
  • The Journal of Physical Chemistry A, Vol. 111, Issue 18
  • DOI: 10.1021/jp0668798

Nitromethane Decomposition under High Static Pressure
journal, July 2010

  • Citroni, Margherita; Bini, Roberto; Pagliai, Marco
  • The Journal of Physical Chemistry B, Vol. 114, Issue 29
  • DOI: 10.1021/jp1035508

Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer: Comparison of Explicit and Implicit Solvent Simulations
journal, June 2012

  • Auer, Benjamin; Soudackov, Alexander V.; Hammes-Schiffer, Sharon
  • The Journal of Physical Chemistry B, Vol. 116, Issue 26
  • DOI: 10.1021/jp3031682

Pulse radiolysis studies of solutions of tetranitromethane in iso-propanol
journal, January 1971

  • Asmus, K. -D.; Chaudhri, Shamim A.; Nazhat, N. B.
  • Transactions of the Faraday Society, Vol. 67
  • DOI: 10.1039/tf9716702607

Proton transfer in solution: Molecular dynamics with quantum transitions
journal, September 1994

  • Hammes‐Schiffer, Sharon; Tully, John C.
  • The Journal of Chemical Physics, Vol. 101, Issue 6
  • DOI: 10.1063/1.467455

Photoconductivities from band states and a dissipative electron dynamics: Si(111) without and with adsorbed Ag clusters
journal, January 2016

  • Vazhappilly, Tijo; Hembree, Robert H.; Micha, David A.
  • The Journal of Chemical Physics, Vol. 144, Issue 2
  • DOI: 10.1063/1.4938560
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Multistate hybrid time-dependent density functional theory with surface hopping accurately captures ultrafast thymine photodeactivation
    journal, January 2019

    • Parker, Shane M.; Roy, Saswata; Furche, Filipp
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 35
    • DOI: 10.1039/c9cp03127h

    Molecular dynamics of reactions between (4,0) zigzag carbon nanotube and hydrogen peroxide under extreme conditions
    journal, January 2018

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: