Furan Fragmentation in the Gas Phase: New Insights from Statistical and Molecular Dynamics Calculations

Erdmann, Ewa; Labuda, Marta; Aguirre, Nestor F.; Diaz-Tendero, Sergio; Alcami, Manuel

doi:10.1021/acs.jpca.8b00881

Furan Fragmentation in the Gas Phase: New Insights from Statistical and Molecular Dynamics Calculations

Journal Article · Thu Mar 15 00:00:00 EDT 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b00881· OSTI ID:1438121

Erdmann, Ewa ^[1]; ^[1]; Aguirre, Nestor F. ^[2]; Diaz-Tendero, Sergio ^[3]; ^[4]

Gdansk Univ. of Technology, Narutowicza (Poland)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. Autonoma de Madrid (Spain)
Univ. Autonoma de Madrid (Spain)
IMDEA Nanosciencia, Madrid (Spain); Univ. Autonoma de Madrid (Spain)

We present a complete exploration of the different fragmentation mechanisms of furan (C₄H₄O) operating at low and high energies. Three different theoretical approaches are combined to determine the structure of all possible reaction intermediates, many of them not described in previous studies, and a large number of pathways involving three types of fundamental elementary mechanisms: isomerization, fragmentation, and H/H₂ loss processes (this last one was not yet explored). Our results are compared with the existing experimental and theoretical investigations for furan fragmentation. At low energies the first processes to appear are isomerization, which always implies the breaking of one C–O bond and one or several hydrogen transfers; at intermediate energies the fragmentation of the molecular skeleton becomes the most relevant mechanism; and H/H₂ loss is the dominant processes at high energy. However, the three mechanisms are active in very wide energy ranges and, therefore, at most energies there is a competition among them.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1438121

Report Number(s):: LA-UR-18-20800

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: 16 Vol. 122; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Theoretical investigation of unimolecular decomposition channels of furan4 Liu, Ruifeng; Zhou, Xuefeng; Zhai, Lei Journal of Computational Chemistry, Vol. 19, Issue 2 https://doi.org/10.1002/(SICI)1096-987X(19980130)19:2<240::AID-JCC17>3.0.CO;2-L	journal	January 1998
Direct, High-Yield Conversion of Cellulose into Biofuel Mascal, Mark; Nikitin, Edward B. Angewandte Chemie International Edition, Vol. 47, Issue 41 https://doi.org/10.1002/anie.200801594	journal	September 2008
A Multicoincidence Study of Fragmentation Dynamics in Collision of γ-Aminobutyric Acid with Low-Energy Ions Capron, Michael; Díaz-Tendero, Sergio; Maclot, Sylvain Chemistry - A European Journal, Vol. 18, Issue 30 https://doi.org/10.1002/chem.201103922	journal	June 2012
Enthalpy of formation and bond energies on unsaturated oxygenated hydrocarbons using G3MP2B3 calculation methods Sebbar, Nadia; Bozzelli, Joseph W.; Bockhorn, Henning International Journal of Chemical Kinetics, Vol. 37, Issue 10 https://doi.org/10.1002/kin.20086	journal	January 2005
Computational chemistry: A useful (sometimes mandatory) tool in mass spectrometry studies: COMPUTATIONAL CHEMISTRY Alcamí, Manuel; Mó, Otilia; Yáñez, Manuel Mass Spectrometry Reviews, Vol. 20, Issue 4 https://doi.org/10.1002/mas.10005	journal	January 2001
Furan in heat-treated foods: Formation, exposure, toxicity, and aspects of risk assessment Moro, Sabrina; Chipman, James Kevin; Wegener, Jan-Willem Molecular Nutrition & Food Research, Vol. 56, Issue 8 https://doi.org/10.1002/mnfr.201200093	journal	May 2012
Ionizing Radiation Damage to DNA Ward, John F. Advances in DNA Damage and Repair https://doi.org/10.1007/978-1-4615-4865-2_35	book	January 1999
The electronic states of furan studied by VUV absorption, near-threshold electron energy-loss spectroscopy and ab initio multi-reference configuration interaction calculations Palmer, Michael H.; Walker, Isobel C.; Ballard, Charles C. Chemical Physics, Vol. 192, Issue 2 https://doi.org/10.1016/0301-0104(94)00386-O	journal	March 1995
The pyrolysis mechanism of furan revisited Liu, Ruifeng; Zhou, Xuefeng; Zuo, Tianming Chemical Physics Letters, Vol. 325, Issue 4 https://doi.org/10.1016/S0009-2614(00)00666-7	journal	July 2000
Synthetic applications of furan Diels-Alder chemistry Oliver Kappe, C.; Shaun Murphree, S.; Padwa, Albert Tetrahedron, Vol. 53, Issue 42 https://doi.org/10.1016/S0040-4020(97)00747-3	journal	October 1997
A study of the unimolecular decomposition of internal-energy-selected furan molecular ions by threshold-photoelectron–photoion coincidence spectroscopy Rennie, E. E.; Cooper, L.; Johnson, C. A. F. Chemical Physics, Vol. 263, Issue 1 https://doi.org/10.1016/S0301-0104(00)00346-3	journal	January 2001
Radiation damage to DNA: The importance of track structure Hill, M. A. Radiation Measurements, Vol. 31, Issue 1-6 https://doi.org/10.1016/S1350-4487(99)00090-6	journal	June 1999
An experimental and kinetic investigation of premixed furan/oxygen/argon flames Tian, Zhenyu; Yuan, Tao; Fournet, René Combustion and Flame, Vol. 158, Issue 4 https://doi.org/10.1016/j.combustflame.2010.12.022	journal	April 2011
New insights into the gas-phase unimolecular fragmentations of [Cysteine–Ca]2+ complexes Hurtado, Marcela; Mó, Otilia; Yáñez, Manuel Computational and Theoretical Chemistry, Vol. 1047 https://doi.org/10.1016/j.comptc.2014.08.015	journal	November 2014
Progress in detailed kinetic modeling of the combustion of oxygenated components of biofuels Tran, Luc Sy; Sirjean, Baptiste; Glaude, Pierre-Alexandre Energy, Vol. 43, Issue 1 https://doi.org/10.1016/j.energy.2011.11.013	journal	July 2012
Charge driven fragmentation of biologically relevant molecules Schlathölter, T.; Hoekstra, R.; Morgenstern, R. International Journal of Mass Spectrometry, Vol. 233, Issue 1-3 https://doi.org/10.1016/j.ijms.2003.12.029	journal	April 2004
Dissociation and fragmentation of furan by electron impact Dampc, Marcin; Zubek, Mariusz International Journal of Mass Spectrometry, Vol. 277, Issue 1-3 https://doi.org/10.1016/j.ijms.2008.04.010	journal	November 2008
Synchrotron-based far-infrared spectroscopy of furan: Rotational analysis of the ν14, ν11, ν18 and ν19 vibrational levels Tokaryk, D. W.; Culligan, S. D.; Billinghurst, B. E. Journal of Molecular Spectroscopy, Vol. 270, Issue 1 https://doi.org/10.1016/j.jms.2011.08.010	journal	November 2011
A review of the occurrence, formation and analysis of furan in heat-processed foods Crews, C.; Castle, L. Trends in Food Science & Technology, Vol. 18, Issue 7 https://doi.org/10.1016/j.tifs.2007.03.006	journal	July 2007
M ₃ C: A Computational Approach To Describe Statistical Fragmentation of Excited Molecules and Clusters Aguirre, Néstor F.; Díaz-Tendero, Sergio; Hervieux, Paul-Antoine Journal of Chemical Theory and Computation, Vol. 13, Issue 3 https://doi.org/10.1021/acs.jctc.6b00984	journal	February 2017
Managing the Computational Chemistry Big Data Problem: The ioChem-BD Platform Álvarez-Moreno, M.; de Graaf, C.; López, N. Journal of Chemical Information and Modeling, Vol. 55, Issue 1 https://doi.org/10.1021/ci500593j	journal	December 2014
Thermal reactions of cyclic ethers at high temperatures. III. Pyrolysis of furan behind reflected shocks Lifshitz, Assa; Bidani, Menashe; Bidani, Shimon The Journal of Physical Chemistry, Vol. 90, Issue 21 https://doi.org/10.1021/j100412a096	journal	October 1986
Polyfuran: a new synthetic approach and electronic properties Glenis, S.; Benz, M.; LeGoff, E. Journal of the American Chemical Society, Vol. 115, Issue 26 https://doi.org/10.1021/ja00079a035	journal	December 1993
Gas-Phase Deprotonation of Uracil−Cu ²⁺ and Thiouracil−Cu ²⁺ Complexes Lamsabhi, Al Mokhtar; Alcamí, Manuel; Mó, Otilia The Journal of Physical Chemistry A, Vol. 110, Issue 5 https://doi.org/10.1021/jp055163u	journal	January 2006
Looking at Radiation Damage on Prebiotic Building Blocks Bacchus-Montabonel, Marie-Christine The Journal of Physical Chemistry A, Vol. 117, Issue 51 https://doi.org/10.1021/jp4102948	journal	December 2013
Unimolecular Fragmentation Induced By Low-Energy Collision: Statistically or Dynamically Driven? Martín-Sómer, Ana; Yáñez, Manuel; Gaigeot, Marie-Pierre The Journal of Physical Chemistry A, Vol. 118, Issue 46 https://doi.org/10.1021/jp5076059	journal	October 2014
Thermal Decomposition of Furan Generates Propargyl Radicals Vasiliou, AnGayle; Nimlos, Mark R.; Daily, John W. The Journal of Physical Chemistry A, Vol. 113, Issue 30 https://doi.org/10.1021/jp903401h	journal	July 2009
Pyrolysis of Furan at Low Pressures: Vibrational Relaxation, Unimolecular Dissociation, and Incubation Times Fulle, D.; Dib, A.; Kiefer, J. H. The Journal of Physical Chemistry A, Vol. 102, Issue 38 https://doi.org/10.1021/jp9823042	journal	September 1998
Pyrolysis of Furan: Ab Initio Quantum Chemical and Kinetic Modeling Studies Sendt, Karina; Bacskay, George B.; Mackie, John C. The Journal of Physical Chemistry A, Vol. 104, Issue 9 https://doi.org/10.1021/jp993537b	journal	March 2000
Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates Román-Leshkov, Yuriy; Barrett, Christopher J.; Liu, Zhen Y. Nature, Vol. 447, Issue 7147, p. 982-985 https://doi.org/10.1038/nature05923	journal	June 2007
Effect of Ni( ii ), Cu( ii ) and Zn( ii ) association on the keto-enol tautomerism of thymine in the gas phase Rincón, Elizabeth; Yáñez, Manuel; Toro-Labbé, Alejandro Phys. Chem. Chem. Phys., Vol. 9, Issue 20 https://doi.org/10.1039/B618050G	journal	January 2007
Modelling charge transfer processes in C ²⁺ –tetrahydrofuran collision for ion-induced radiation damage in DNA building blocks Erdmann, Ewa; Bacchus-Montabonel, Marie-Christine; Łabuda, Marta Physical Chemistry Chemical Physics, Vol. 19, Issue 30 https://doi.org/10.1039/C7CP02100C	journal	January 2017
Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals Schlegel, H. Bernhard; Millam, John M.; Iyengar, Srinivasan S. The Journal of Chemical Physics, Vol. 114, Issue 22 https://doi.org/10.1063/1.1372182	journal	June 2001
Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals. II. Generalizations based on mass-weighting, idempotency, energy conservation and choice of initial conditions Iyengar, Srinivasan S.; Schlegel, H. Bernhard; Millam, John M. The Journal of Chemical Physics, Vol. 115, Issue 22 https://doi.org/10.1063/1.1416876	journal	January 2001
A core-level photoionization study of furan Rennie, E. E.; Hergenhahn, U.; Kugeler, O. The Journal of Chemical Physics, Vol. 117, Issue 14 https://doi.org/10.1063/1.1504435	journal	October 2002
Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals. III. Comparison with Born–Oppenheimer dynamics Schlegel, H. Bernhard; Iyengar, Srinivasan S.; Li, Xiaosong The Journal of Chemical Physics, Vol. 117, Issue 19 https://doi.org/10.1063/1.1514582	journal	November 2002
Theoretical study of the low-lying excited singlet states of furan Gromov, E. V.; Trofimov, A. B.; Vitkovskaya, N. M. The Journal of Chemical Physics, Vol. 119, Issue 2 https://doi.org/10.1063/1.1578051	journal	July 2003
Theoretical study of photoinduced ring-opening in furan Gromov, E. V.; Trofimov, A. B.; Gatti, F. The Journal of Chemical Physics, Vol. 133, Issue 16 https://doi.org/10.1063/1.3493451	journal	October 2010
Ultrafast photodynamics of furan Fuji, Takao; Suzuki, Yoshi-Ichi; Horio, Takuya The Journal of Chemical Physics, Vol. 133, Issue 23 https://doi.org/10.1063/1.3518441	journal	December 2010
The C–H bond dissociation energy of furan: Photoelectron spectroscopy of the furanide anion Vogelhuber, Kristen M.; Wren, Scott W.; Sheps, Leonid The Journal of Chemical Physics, Vol. 134, Issue 6 https://doi.org/10.1063/1.3548873	journal	February 2011
Ab initio quantum dynamical study of photoinduced ring opening in furan Gromov, E. V.; Lévêque, C.; Gatti, F. The Journal of Chemical Physics, Vol. 135, Issue 16 https://doi.org/10.1063/1.3653792	journal	October 2011
The equation of motion coupled‐cluster method. A systematic biorthogonal approach to molecular excitation energies, transition probabilities, and excited state properties Stanton, John F.; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 98, Issue 9 https://doi.org/10.1063/1.464746	journal	May 1993
Resonant dissociation of DNA bases by subionization electrons Huels, Michael A.; Hahndorf, Ina; Illenberger, Eugen The Journal of Chemical Physics, Vol. 108, Issue 4 https://doi.org/10.1063/1.475503	journal	January 1998
A complete basis set model chemistry. VI. Use of density functional geometries and frequencies Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W. The Journal of Chemical Physics, Vol. 110, Issue 6 https://doi.org/10.1063/1.477924	journal	February 1999
Ultraviolet photodissociation of furan probed by tunable synchrotron radiation Sorkhabi, Osman; Qi, Fei; Rizvi, Abbas H. The Journal of Chemical Physics, Vol. 111, Issue 1 https://doi.org/10.1063/1.479257	journal	July 1999
Pyrolysis of furan in a microreactor Urness, Kimberly N.; Guan, Qi; Golan, Amir The Journal of Chemical Physics, Vol. 139, Issue 12 https://doi.org/10.1063/1.4821600	journal	September 2013
Analysis and risk assessment of furan in coffee products targeted to adolescents Waizenegger, J.; Winkler, G.; Kuballa, T. Food Additives & Contaminants: Part A, Vol. 29, Issue 1 https://doi.org/10.1080/19440049.2011.617012	journal	January 2012
Ion-induced ionization and fragmentation of DNA building blocks Schlathölter, Thomas; Alvarado, Fresia; Bari, Sadia Physica Scripta, Vol. 73, Issue 4 https://doi.org/10.1088/0031-8949/73/4/N01	journal	March 2006
Theoretical predictions for ionization cross sections of DNA nucleobases impacted by light ions Champion, C.; Lekadir, H.; Galassi, M. E. Physics in Medicine and Biology, Vol. 55, Issue 20 https://doi.org/10.1088/0031-9155/55/20/002	journal	September 2010
Ionization and fragmentation of furan molecules by electron collisions Dampc, Marcin; Linert, Ireneusz; Zubek, Mariusz Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 48, Issue 16 https://doi.org/10.1088/0953-4075/48/16/165202	journal	July 2015
Ion interaction with biomolecular systems and the effect of the environment Domaracka, Alicja; Capron, Michael; Maclot, Sylvain Journal of Physics: Conference Series, Vol. 373 https://doi.org/10.1088/1742-6596/373/1/012005	journal	July 2012
Electron transfer induced by collision of low-energy doubly charged carbon ions with tetrahydrofuran Erdmann, Ewa; Łabuda, Marta Journal of Physics: Conference Series, Vol. 635, Issue 2 https://doi.org/10.1088/1742-6596/635/2/022097	journal	September 2015
Charge dependence of fragmentation process induced by ion collisions with furan molecule Erdmann, E.; Łabuda, M.; Díaz-Tendero, S. Journal of Physics: Conference Series, Vol. 875 https://doi.org/10.1088/1742-6596/875/11/102021	journal	July 2017
Theoretical treatment of charge-transfer processes induced by collision of C q + ions with uracil Bacchus-Montabonel, M. C.; Łabuda, M.; Tergiman, Y. S. Physical Review A, Vol. 72, Issue 5 https://doi.org/10.1103/PhysRevA.72.052706	journal	November 2005
Fragmentation dynamics of gas-phase furan following K -shell ionization Pešić, Z. D.; Rolles, D.; Dumitriu, I. Physical Review A, Vol. 82, Issue 1 https://doi.org/10.1103/PhysRevA.82.013401	journal	July 2010
Ionization of uracil in collisions with highly charged carbon and oxygen ions of energy 100 keV to 78 MeV Agnihotri, A. N.; Kasthurirangan, S.; Nandi, S. Physical Review A, Vol. 85, Issue 3 https://doi.org/10.1103/PhysRevA.85.032711	journal	March 2012
Fragmentation of protonated oligonucleotides by energetic photons and C q + ions González-Magaña, O.; Tiemens, M.; Reitsma, G. Physical Review A, Vol. 87, Issue 3 https://doi.org/10.1103/PhysRevA.87.032702	journal	March 2013
MOLECULAR BIOLOGY:A Sting in the Tail of Electron Tracks Michael, B. D. Science, Vol. 287, Issue 5458 https://doi.org/10.1126/science.287.5458.1603	journal	March 2000
Resonant Formation of DNA Strand Breaks by Low-Energy (3 to 20 eV) Electrons Boudaïffa, B. Science, Vol. 287, Issue 5458 https://doi.org/10.1126/science.287.5458.1658	journal	March 2000
Interactions of protons with furan molecules studied by collision-induced emission spectroscopy at the incident energy range of 50–1000 eV Wasowicz, Tomasz J.; Pranszke, Boguslaw The European Physical Journal D, Vol. 70, Issue 8 https://doi.org/10.1140/epjd/e2016-70308-1	journal	August 2016

Cited By (6)

Charge Transfer, Complexes Formation and Furan Fragmentation Induced by Collisions with Low-Energy Helium Cations Wasowicz, Tomasz J.; Łabuda, Marta; Pranszke, Boguslaw International Journal of Molecular Sciences, Vol. 20, Issue 23 https://doi.org/10.3390/ijms20236022	journal	November 2019
Dissociation dynamics of the diamondoid adamantane upon photoionization by XUV femtosecond pulses Maclot, Sylvain; Lahl, Jan; Peschel, Jasper arXiv https://doi.org/10.48550/arxiv.2001.03373	text	January 2020
Ground‐state dissociation pathways for the molecular cation of 2‐chlorothiophene: A time‐of‐flight mass spectrometry and computational study Upadhyaya, Hari P. Rapid Communications in Mass Spectrometry, Vol. 33, Issue 20 https://doi.org/10.1002/rcm.8497	journal	August 2019
Mechanistic investigation of CO generation by pyrolysis of furan and its main derivatives Sun, Baizhong; Liang, Honglin; Che, Deyong RSC Advances, Vol. 9, Issue 16 https://doi.org/10.1039/c8ra10106j	journal	January 2019
Fully versus constrained statistical fragmentation of carbon clusters and their heteronuclear derivatives Aguirre, Néstor F.; Díaz-Tendero, Sergio; IdBarkach, Tijani The Journal of Chemical Physics, Vol. 150, Issue 14 https://doi.org/10.1063/1.5083864	journal	April 2019
Absolute ionization and dissociation cross sections of tetrahydrofuran: Fragmentation-ion production mechanisms Wolff, W.; Rudek, B.; da Silva, L. A. The Journal of Chemical Physics, Vol. 151, Issue 6 https://doi.org/10.1063/1.5115403	journal	August 2019

Similar Records

Very low pressure pyrolysis of furan, 2-methylfuran, and 2,5-dimethylfuran. The stability of the furan ring

Journal Article · Wed Jan 02 23:00:00 EST 1985 · J. Phys. Chem.; (United States) · OSTI ID:5786297

Decomposition of Furan on Pd(111)

Journal Article · Sat Dec 31 23:00:00 EST 2011 · Topics in Catalysis · OSTI ID:1040749

Electron-impact vibrational excitation of furan

Journal Article · Wed Dec 14 23:00:00 EST 2011 · Physical Review. A · OSTI ID:22095612

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Fragmentation
Furan
DFT
M3C
ADMP
Inorganic and Physical Chemistry

Furan Fragmentation in the Gas Phase: New Insights from Statistical and Molecular Dynamics Calculations

Citation Formats

References (60)

Cited By (6)

Similar Records

Related Subjects