Computational investigation on the reaction of dimethyl ether with nitric dioxide. I. Underlying mechanism and accurate energetics

  • Yulei GuanEmail author
  • Ru Liu
  • Junpeng Lou
  • Haixia Ma
  • Jirong Song
Regular Article


The reaction of dimethyl ether (DME) with nitrogen dioxide (NO2), which plays a critical role in the low-temperature oxidation behavior of DME, is employed as prototype for reactions of heavier clean ether fuels to assess different hybrid density functionals and “double-hybrid” density functionals. The reaction energies and barrier heights for the reaction system were computed with CCSD(T) theory extrapolated to the complete basis set limit using augmented cc-pVDZ and cc-pVTZ basis sets. The involved energetics were also improved by the CCSD(T)/6-311+G(2df,2p), QCISD(T)/6-311+G(2df,2p), G3B3, G3MP2B3, CBS-QB3, G4, and G4MP2 calculations. It is shown that “double-hybrid” density functionals with the TZVP basis set can give accurate geometries and principal moments of inertia of reactants and products and the B2PLYP/TZVP level can achieve results for barrier heights comparable in accuracy to the high-level ab initio results, which is identified as an important potential theoretical level for direct kinetics studies on the rates of these and homologous reaction systems. The calculated results indicate that NO2 preferentially captures an out-of-plane hydrogen atom from the DME molecule by the O or the N end via three distinct channels to produce trans-HONO, cis-HONO, and HNO2, respectively, and each channel involves the formation of a van der Waals post-reaction adducts lying lower in energy than their separate products.


Dimethyl ether Nitrogen dioxide Hydrogen abstraction Multi-reference diagnostics Reaction mechanism Computational chemistry 



This work was supported by the National Natural Science Foundation of China (No. 21606178).


  1. 1.
    Kohse-Höinghaus K, Oßwald P, Cool TA, Kasper T, Hansen N, Qi F, Westbrook CK, Westmoreland PR (2010) Biofuel combustion chemistry: from ethanol to biodiesel. Angew Chem Int Ed 49:3572–3597CrossRefGoogle Scholar
  2. 2.
    Ribeiro NM, Pinto AC, Quintella CM, da Rocha GO, Teixeira LSG, Guarieiro LLN, do Carmo Rangel M, Veloso MCC, Rezende MJC, da Cruz RS, de Oliveira AM, Torres EA, de Andrade JB (2007) The role of additives for diesel and diesel blended (ethanol or biodiesel) fuels: a review. Energy Fuels 21:2433–2445CrossRefGoogle Scholar
  3. 3.
    Arcoumanis C, Bae C, Crookes R, Kinoshita E (2008) The potential of di-methyl ether (DME) as an alternative fuel for compression-ignition engines: a review. Fuel 87:1014–1030CrossRefGoogle Scholar
  4. 4.
    Miller JA, Bowman CT (1989) Mechanism and modeling of nitrogen chemistry in combustion. Prog Energy Combust Sci 15:287–338CrossRefGoogle Scholar
  5. 5.
    Alzueta MU, Muro J, Bilbao R, Glarborg P (1999) Oxidation of dimethyl ether and its interaction with nitrogen oxides. Isr J Chem 39:73–86CrossRefGoogle Scholar
  6. 6.
    Dagaut P, Lucheke J, Cathonnet M (2001) The low temperature oxidation of DME and mutual sensitization of the oxidation of DME and nitric oxide: experimental and detailed kinetic modeling. Combust Sci Technol 165:61–84CrossRefGoogle Scholar
  7. 7.
    Ye W, Shi JC, Zhang RT, Wu XJ, Zhang X, Qi ML, Luo SN (2016) Experimental and kinetic modeling study of CH3OCH3 ignition sensitized by NO2. Energy Fuels 30:10900–10908CrossRefGoogle Scholar
  8. 8.
    Chan WT, Heck SM, Pritchard HO (2001) Reaction of nitrogen dioxide with hydrocarbons and its influence on spontaneous ignition. A computational study. Phys Chem Chem Phys 3:56–62CrossRefGoogle Scholar
  9. 9.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA et al (2009) Gaussian 09, revision A.02. Gaussian, Inc., WallingfordGoogle Scholar
  10. 10.
    Boese AD, Martin JML (2004) Development of density functionals for thermochemical kinetics. J Chem Phys 121:3405–3416CrossRefPubMedGoogle Scholar
  11. 11.
    Lynch BJ, Fast PL, Harris M, Truhlar DG (2000) Adiabatic connection for kinetics. J Phys Chem A 104:811–4815CrossRefGoogle Scholar
  12. 12.
    Zhao Y, Truhlar DG (2004) Hybrid meta density functional theory methods for thermochemistry, thermochemical kinetics, and noncovalent interactions: the MPW1B95 and MPWB1K models and comparative assessments for hydrogen bonding and van der Waals interactions. J Phys Chem A 108:6908–6918CrossRefGoogle Scholar
  13. 13.
    Chai JD, Head-Gordon M (2008) Systematic optimization of long-range corrected hybrid density functional. J Chem Phys 128:084106/1–15CrossRefGoogle Scholar
  14. 14.
    Chai JD, Head-Gordon M (2008) Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections. Phys Chem Chem Phys 10:6615–6620CrossRefGoogle Scholar
  15. 15.
    Zhao Y, Schultz NE, Truhlar DG (2005) Exchange-correlation functional with broad accuracy for metallic and nonmetallic compounds, kinetics, and noncovalent interactions. J Chem Phys 123:161103/1–4Google Scholar
  16. 16.
    Zhao Y, Schultz NE, Truhlar DG (2006) Design of density functionals by combining the method of constraint satisfaction with parameterization for thermochemistry, thermochemical kinetics, and noncovalent interactions. J Chem Theory Comput 2:364–382CrossRefPubMedGoogle Scholar
  17. 17.
    Zhao Y, Truhlar DG (2006) Comparative DFT study of van der Waals complexes: rare-gas dimers, alkaline-earth dimers, zinc dimer, and zinc-rare-gas dimmers. J Phys Chem A 110:5121–5129CrossRefPubMedGoogle Scholar
  18. 18.
    Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Acc 120:215–241CrossRefGoogle Scholar
  19. 19.
    Zhao Y, Truhlar DG (2006) A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions. J Chem Phys 125:194101/1–18Google Scholar
  20. 20.
    Schäfer A, Huber C, Ahlrichs R (1994) Fully optimized contracted gaussian basis sets of triple zeta valence quality for atoms Li to Kr. J Chem Phys 100:5829–5835CrossRefGoogle Scholar
  21. 21.
    Lynch BJ, Zhao Y, Truhlar DG (2003) Effectiveness of diffuse basis functions for calculating relative energies by density functional theory. J Phys Chem A 107:1384–1388CrossRefGoogle Scholar
  22. 22.
    Zheng J, Zhao Y, Truhlar DG (2009) The DBH24/08 database and its use to assess electronic structure model chemistries for chemical reaction barrier heights. J Chem Theory Comput 5:808–821CrossRefPubMedGoogle Scholar
  23. 23.
    Zhao Y, Truhlar DG (2008) Density functionals with broad applicability in chemistry. Acc Chem Res 41:157–167CrossRefPubMedGoogle Scholar
  24. 24.
    Grimme S (2006) Semiempirical hybrid density functional with perturbative second-order correlation. J Chem Phys 124:034108/1–16CrossRefGoogle Scholar
  25. 25.
    Schwabe T, Grimme S (2007) Double-hybrid density functionals with long-range dispersion corrections: higher accuracy and extended applicability. Phys Chem Chem Phys 9:3397–3406CrossRefPubMedGoogle Scholar
  26. 26.
    Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104/1–19CrossRefGoogle Scholar
  27. 27.
    Grimme S (2011) Density functional theory with london dispersion corrections. Wiley Interdiscip Rev Comput Mol Sci 1:211–228CrossRefGoogle Scholar
  28. 28.
    Schwabe T, Grimme S (2006) Towards chemical accuracy for the thermodynamics of large molecules: new hybrid density functionals including non-local correlation effects. Phys Chem Chem Phys 8:4398–4401CrossRefPubMedGoogle Scholar
  29. 29.
    Hratchian HP, Schlegel HB (2004) Accurate reaction paths using a Hessian based predictor–corrector integrator. J Chem Phys 120:9918–9924CrossRefPubMedGoogle Scholar
  30. 30.
    Hratchian HP, Schlegel HB (2005) Using Hessian updating to increase the efficiency of a Hessian based predictor–corrector reaction path following method. J Chem Theory Comput 1:61–69CrossRefPubMedGoogle Scholar
  31. 31.
    Purvis GD III, Bartlett RJ (1982) A full coupled-cluster singles and doubles model: the inclusion of disconnected triples. J Chem Phys 76:1910–1918CrossRefGoogle Scholar
  32. 32.
    Scuseria GE, Janssen CL, Schaefer HF III (1988) An efficient reformulation of the closed-shell coupled cluster single and double excitation (CCSD) equations. J Chem Phys 89:7382–7387CrossRefGoogle Scholar
  33. 33.
    Gauss J, Cremer D (1988) Analytical evaluation of energy gradients in quadratic configuration-interaction theory. Chem Phys Lett 150:280–286CrossRefGoogle Scholar
  34. 34.
    Pople JA, Head-Gordon M, Raghavachari K (1987) Quadratic configuration interaction—a general technique for determining electron correlation energies. J Chem Phys 87:5968–5975CrossRefGoogle Scholar
  35. 35.
    Dunning TH Jr (1989) Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. J Chem Phys 90:1007–1023CrossRefGoogle Scholar
  36. 36.
    Kendall RA, Dunning TH Jr, Harrison RJ (1992) Electron affinities of the first-row atoms revisited. Systematic basis sets and wave functions. J Chem Phys 96:6796–6806CrossRefGoogle Scholar
  37. 37.
    Woon DE, Dunning TH Jr (1993) Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon. J Chem Phys 98:1358–1371CrossRefGoogle Scholar
  38. 38.
    Schwenke DW (2005) The extrapolation of one-electron basis set in electronic structure calculations: how it should work and how it can be made to work. J Phys Chem 122:014107/1–7CrossRefGoogle Scholar
  39. 39.
    Baboul AG, Curtiss LA, Redfern PC, Raghavachari K (1999) Gaussian-3 theory using density functional geometries and zero-point energies. J Chem Phys 110:7650–7657CrossRefGoogle Scholar
  40. 40.
    Montgomery JA Jr, Frisch MJ, Ochterski JW, Petersson GA (1999) A complete basis set model chemistry. VI. Use of density functional geometries and frequencies. J Chem Phys 110:2822–2827CrossRefGoogle Scholar
  41. 41.
    Curtiss LA, Redfern PC, Raghavachari K (2007) Gaussian-4 theory. J Chem Phys 126:084108/1–12CrossRefGoogle Scholar
  42. 42.
    Curtiss LA, Redfern PC, Raghavachari K (2007) Gaussian-4 theory using reduced order perturbation theory. J Chem Phys 127:124105/1–8CrossRefGoogle Scholar
  43. 43.
    Boys SF, Bernardi F (1970) Calculation of small molecular interactions by differences of separate total energies-some procedures with reduced errors. Mol Phys 19:553–566CrossRefGoogle Scholar
  44. 44.
    Lee TJ, Taylor PR (1989) A diagnostic for determining the quality of single-reference electron correlation methods. Int J Quantum Chem 23:199–207Google Scholar
  45. 45.
    Zhao Y, Tishchenko O, Gour JR, Li W, Lutz JJ, Piecuch P, Truhlar DG (2009) Thermochemical kinetics for multireference systems: addition reactions of ozone. J Phys Chem A 113:5786–5799CrossRefPubMedGoogle Scholar
  46. 46.
    Karton A, Rabinovich E, Martin JML, Ruscic B (2006) W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions. J Chem Phys 125:144108/1–17Google Scholar
  47. 47.
    Rienstra-Kiracofe JC, Allen WD, Schaefer HF III (2000) The C2H5 + O2 reaction mechanism: high-level ab initio characterizations. J Phys Chem A 104:9823–9840CrossRefGoogle Scholar
  48. 48.
    Peiró-García J, Nebot-Gil I (2003) Ab initio study of the mechanism of the atmospheric reaction: NO2 + O3 → NO3 + O2. J Comput Chem 24:1657–1663CrossRefPubMedGoogle Scholar
  49. 49.
    Peiró-García J, Nebot-Gil I (2003) Ab initio study on the mechanism of the atmospheric reaction OH + O3 → HO2 + O2. ChemPhysChem 4:843–847CrossRefPubMedGoogle Scholar
  50. 50.
    Lambert N, Kaltsoyannis N, Price SD, Žabka J, Herman Z (2006) Bond-forming reactions of dications with molecules: a computational and experimental study of the mechanisms for the formation of HCF2+ from CF3 2+ and H2. J Phys Chem A 110:2898–2905CrossRefPubMedGoogle Scholar
  51. 51.
    Feller D, Peterson KA, Dixon DA (2008) A survey of factors contributing to accurate theoretical predictions of atomization energies and molecular structures. J Chem Phys 129:204105/1–32CrossRefGoogle Scholar
  52. 52.
    Sullivan MB, Iron MA, Redfern PC, Martin JML, Curtiss LA, Radom L (2003) Heats of formation of alkali metal and alkaline earth metal oxides and hydroxides: surprisingly demanding targets for high-level ab initio procedures. J Phys Chem A 107:5617–5630CrossRefGoogle Scholar
  53. 53.
    Johnson III RD (2018) Computational chemistry comparison and benchmark database, version 18; National Institute of Standards and Technology. Accessed 19 Oct 2018
  54. 54.
    Alecu IM, Zheng J, Zhao Y, Truhlar DG (2010) Computational thermochemistry: scale factor databases and scale factors for vibrational frequencies obtained from electronic model chemistries. J Chem Theory Comput 6:2872–2887CrossRefPubMedGoogle Scholar
  55. 55.
    Kesharwani MK, Brauer B, Martin JML (2015) Frequency and zero-point vibrational energy scale factors for double-hybrid density functionals (and other selected methods): can anharmonic force fields be avoided? J Phys Chem A 119:1701–1714CrossRefPubMedGoogle Scholar
  56. 56.
    Xiao CX, Yan N, Zou M, Hou SC, Kou Y, Liu W, Zhang S (2006) NO2-catalyzed deep oxidation of methanol: experimental and theoretical studies. J Mol Catal A Chem 252:202–211CrossRefGoogle Scholar
  57. 57.
    Miller AR (1978) A theoretical relation for the position of the energy barrier between initial and final states of chemical reactions. J Am Chem Soc 100:1984–1992CrossRefGoogle Scholar
  58. 58.
    Chai J, Goldsmith CF (2017) Rate coefficients for fuel + NO2: predictive kinetics for HONO and HNO2 formation. Proc Combust Inst 36:617–626CrossRefGoogle Scholar
  59. 59.
    Anastasi C, Hancock DU (1988) NO2 kinetic studies using laser-induced fluorescence. J Chem Soc Faraday Trans 2 84(10):1697–1706CrossRefGoogle Scholar
  60. 60.
    Koda S, Tanaka M (1986) Ignition of premixed methanol/air in a heated flow tube and the effect of NO2 addition. Combust Sci Technol 47:165–176CrossRefGoogle Scholar
  61. 61.
    Tranter RS, Lynch PT, Yang X (2013) Dissociation of dimethyl ether at high temperatures. Proc Combust Inst 34:591–598CrossRefGoogle Scholar
  62. 62.
    Guan Y, Gao J, Song Y, Li Y, Ma H, Song J (2017) Variational effect and anharmonic torsion on kinetic modeling for initiation reaction of dimethyl ether combustion. J Phys Chem A 121:1121–1132CrossRefPubMedGoogle Scholar
  63. 63.
    Ruscic B, Bross DH (2018) Active Thermochemical Tables (ATcT) Values Based on Version 1.122 of the Thermochemical Network. Accessed 15 Dec 2018
  64. 64.
    Asatryan R, Bozzelli JW, Simmie JM (2007) Thermochemistry for enthalpies and reaction paths of nitrous acid isomers. Int J Chem Kinet 39:378–398CrossRefGoogle Scholar
  65. 65.
    Guan Y, Lou J, Liu R, Ma H, Song J (2018) Thermodynamic properties of the methylmethoxy radical with intricate treatment of two-dimensional hindered internal rotations. J Chem Eng Data 63:3640–3649CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Yulei Guan
    • 1
    Email author
  • Ru Liu
    • 1
  • Junpeng Lou
    • 1
  • Haixia Ma
    • 1
  • Jirong Song
    • 1
  1. 1.School of Chemical EngineeringNorthwest UniversityXi’anChina

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