Skip to main content
SpringerLink
Log in

Protonation sites in methyl nitrate and the formation of transient CH4NO3 radicals. A neutralization—reionization mass spectrometric and computational study

  • Published:
Journal of the American Society for Mass Spectrometry

Abstract

Protonation sites in methyl nitrate (1) were evaluated computationally at the Gaussian 2(MP2) level of ab initio theory. The methoxy oxygen was the most basic site that had a calculated proton affinity of PA = 728–738 kJ mol−1 depending on the optimization method used to calculate the equilibrium geometry of the CH3O(H)-NO +2 ion (2+). Protonation at the terminal oxygen atoms in methyl nitrate was less exothermic; the calculated proton affinities were 725, 722, and 712 kJ mol−1 for the formation of the syn-syn, anti-syn, and syn-anti ion rotamers 3a+, 3b+, and 3c+, respectively. Ion 2+ was prepared by an ion-molecule reaction of NO +2 with methanol and used to generate the transient CH3O(H)-NO .2 radical (2) by femtosecond collisional electron transfer. Exothermic protonation of 1 produced a mixture of 3a+–3c+ with 2+ that was used to generate transient radicals 3a–3c. Radical 2 was found to be unbound and dissociated without barrier to methanol and NO2. Radicals 3a–3c were calculated to be weakly bound. When formed by vertical neutralization, 3a–3c dissociated completely on the 4.2 μs time scale of the experiment. The main dissociations of 3a–3c were formations of CH3O. + HONO and CH3ONO + OH.. The gas-phase chemistry of radicals 3a–3c and their dissociation products, as studied by neutralization—reionization mass spectrometry, was dominated by Franck—Condon effects on collisional neutralization and reionization. The adiabatic ionization energies of 3a–3c were calculated as 7.54, 7.57, and 7.66 eV, respectively.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Atkinson, R. Journal Physical Chemistry and Reference Data, Monograph 2; American Institute of Physics: Woodbury, NY, 1994; p 139.

    Google Scholar 

  2. Nielsen, O. J.; Sidebottom, H. W.; Donlon, M.; Treacy, J. Int. J. Chem. Kinet. 1991, 23, 1095.

    Article  CAS  Google Scholar 

  3. Combustion Chemistry; Gardiner, W. C., Jr., Ed.; Springer: New York, 1984.

    Google Scholar 

  4. Egsgaard, H. Ion Chemistry of the Flame, Department of Combustion Research, Risø National Laboratory: Roskilde, Denmark, 1993.

    Google Scholar 

  5. Brill, T. B.; James, K. J. Chem. Rev. 1993, 93, 2667.

    Article  CAS  Google Scholar 

  6. Organic Energetic Compounds; Marinkas, P. L., Ed.; Nova Science Publ.: Commack, NY, 1996.

    Google Scholar 

  7. Akhavan, J. The Chemistry of Explosives; Royal Society of Chemistry: Cambridge, 1998.

    Google Scholar 

  8. Carr, R. W. In Advances in Photochemistry; Neckers, D. C.; Volman, D. H.; von Bünau, G., Eds.; Wiley: New York, 1999; Vol. 25, pp 1–57.

    Chapter  Google Scholar 

  9. Atkinson, R.; Baulch, D. L.; Cox, R. A.; Hampson, R. F., Jr.; Kerr, J. A.; Troe, J. J. Phys. Chem. Ref. Data 1992, 21, 1125.

    Article  CAS  Google Scholar 

  10. Burgers, P. C.; Holmes, J. L.; Mommers, A.; Terlouw, J. K. Chem. Phys. Lett. 1983, 102, 1.

    Article  CAS  Google Scholar 

  11. Danis, P. O.; Wesdemiotis, C.; McLafferty, F. W. J. Am. Chem. Soc. 1983, 105, 7454.

    Article  CAS  Google Scholar 

  12. For recent reviews see: Goldberg, N.; Schwarz, H. Acc. Chem. Res. 1994, 27, 347.

    Article  CAS  Google Scholar 

  13. Schalley, C. A.; Hornung, G.; Schroder, D.; Schwarz, H. Chem. Soc. Rev. 1998, 27, 91.

    Article  CAS  Google Scholar 

  14. Turecek, F. J. Mass Spectrom. 1998, 33, 779.

    Article  CAS  Google Scholar 

  15. Zagorevskii, D.; Holmes, J. L. Mass Spectrom. Rev. 1999, 18, 87.

    Article  CAS  Google Scholar 

  16. Kuhns, D. W.; Shaffer, S. A.; Tran, T. B.; Turecek, F. J. Phys. Chem. 1994, 98, 4845.

    Article  CAS  Google Scholar 

  17. Kuhns, D. W.; Turecek, F. Org. Mass Spectrom. 1994, 29, 463.

    Article  CAS  Google Scholar 

  18. Sadilek, M.; Turecek, F. J. Phys. Chem. 1996, 100, 224.

    Article  CAS  Google Scholar 

  19. Sadilek, M.; Turecek, F. Chem. Phys. Lett. 1996, 263, 203.

    Article  CAS  Google Scholar 

  20. Nguyen, V. Q.; Sadilek, M.; Frank, A. J.; Ferrier, J. G.; Turecek, F. J. Phys. Chem. A 1997, 101, 3789.

    Article  CAS  Google Scholar 

  21. Turecek, F.; Gu, M.; Shaffer, S. A. J. Am. Soc. Mass Spectrom. 1992, 3, 493.

    Article  CAS  Google Scholar 

  22. Black, A. P.; Babers, F. H. Org. Synth. 1939, 19, 64.

    CAS  Google Scholar 

  23. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.6, Gaussian, Inc., Pittsburgh, PA, 1998.

    Google Scholar 

  24. Becke, A. D. J. Chem. Phys. 1993, 98, 1372, 5648.

    Article  CAS  Google Scholar 

  25. Stephens, P. J.; Devlin, F. J.; Chablowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.

    Article  CAS  Google Scholar 

  26. Møller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618.

    Article  Google Scholar 

  27. Mayer, I. Adv. Quantum Chem. 1980, 12, 189.

    Article  CAS  Google Scholar 

  28. Schlegel, H. B. J. Chem. Phys. 1986, 84, 4530.

    Article  CAS  Google Scholar 

  29. For the various frequency correction factors see for example: Rauhut, G.; Pulay, R. J. Phys. Chem. 1995, 99, 3093.

    Article  CAS  Google Scholar 

  30. Finley, J. W.; Stephens, P. J. J. Mol. Struct. (THEOCHEM) 1995, 227, 357.

    Google Scholar 

  31. Wong, M. W. Chem. Phys. Lett. 1996, 256, 391.

    Article  CAS  Google Scholar 

  32. Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502.

    Article  CAS  Google Scholar 

  33. Curtiss, L. A.; Raghavachari, K.; Pople, J. A. J. Chem. Phys. 1993, 98, 1293.

    Article  CAS  Google Scholar 

  34. Zhu, L.; Hase, W. L. Quantum Chemistry Program Exchange; Indiana University: Bloomington, IN, 1994; Program No. QCPE 644.

    Google Scholar 

  35. Frank, A. J.; Sadilek, M.; Ferrier, J. G.; Turecek, F. J. Am. Chem. Soc. 1997, 119, 12343.

    Article  CAS  Google Scholar 

  36. Nguyen, V. Q.; Turecek, F. J. Mass Spectrom. 1996, 31, 1173–1184.

    Article  CAS  Google Scholar 

  37. Nguyen, V. Q.; Turecek, F. J. Am. Chem. Soc. 1997, 119, 2280.

    Article  CAS  Google Scholar 

  38. Wolken, J. K.; Turecek, F. J. Am. Chem. Soc. 1999, 121, 6010.

    Article  CAS  Google Scholar 

  39. Wolken, J. K.; Turecek, F. J. Phys. Chem. A 1999, 103, 6268.

    Article  CAS  Google Scholar 

  40. Attina, M.; Cacace, F.; Yanez, M. J. Am. Chem. Soc. 1987, 109, 5092.

    Article  CAS  Google Scholar 

  41. de Petris, G. Org. Mass Spectrom. 1990, 25, 83.

    Article  Google Scholar 

  42. Lee, T. J.; Rice, J. E. J. Am. Chem. Soc. 1992, 114, 8247.

    Article  CAS  Google Scholar 

  43. Glaser, R.; Choy, G. S.-C. J. Org. Chem. 1992, 57, 4976.

    Article  CAS  Google Scholar 

  44. Bernardi, F.; Cacace, F.; Grandinetti, F. J. Chem. Soc. Perkin Trans. 2 1989, 413.

    Google Scholar 

  45. NIST Chemistry Webbook, NIST Standard Reference Database, No. 69; Mallard, W. G.; Lindstrom, P. J., Eds.; NIST: Gaithersburg, MD, 1998; http://webbook.nist.gov/chemistry.

    Google Scholar 

  46. Harrison, A. G. Chemical Ionization Mass Spectrometry; CRC: Boca Raton, FL, 1992; p 10.

    Google Scholar 

  47. Uggerud, E. Adv. Mass Spectrom. 1995, 13, 53.

    CAS  Google Scholar 

  48. Pollik, W. F.; Guyer, D. R.; Moore, C. B. J. Chem. Phys. 1990, 92, 3453.

    Article  Google Scholar 

  49. Hase, W. L. Acc. Chem. Res. 1998, 31, 659.

    Article  CAS  Google Scholar 

  50. Vallance, C.; Maclagan, R. G. A. R.; Harland, P. W. J. Phys. Chem. A 1997, 101, 3505.

    Article  CAS  Google Scholar 

  51. Bartmess, J. E.; Georgiadis, R. M. Vacuum 1983, 33, 149.

    Article  CAS  Google Scholar 

  52. McLafferty, F. W.; Stauffer, D. B. The Wiley/NBS Registry of Mass Spectral Data; Wiley: New York, 1989; Vol. 1, p 13 [598-58-3].

    Google Scholar 

  53. Polasek, M.; Turecek, F. J. Phys. Chem. A 1999, 103, 9241.

    Article  CAS  Google Scholar 

  54. Egsgaard, H.; Carlsen, L.; Florencio, H.; Drewello, T.; Schwarz, H. Ber. Bunsenges. Phys. Chem. 1989, 93, 76.

    CAS  Google Scholar 

  55. O’Connor, C. S. S.; Jones, N. C.; Price, S. D. Int. J. Mass Spectrom. 1997, 163, 131.

    Article  Google Scholar 

  56. Leeck, D. T.; Kenttamaa, H. I. Org. Mass Spectrom. 1994, 29, 106.

    Article  CAS  Google Scholar 

  57. Laidler, K. J.; Polanyi, J. C. In Progress in Reaction Kinetics; Porter, G., Ed.; Pergamon: Oxford, 1965; Vol. 3, pp 3–61.

    Google Scholar 

  58. Levine, I. N. Physical Chemistry, 3rd ed.; McGraw-Hill: New York, 1988; pp 783–796.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Washington, Bagley Hall, Box 351700, 98195-1700, Seattle, WA

    Miroslav Polášek & František Tureček

Authors
  1. Miroslav Polášek
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. František Tureček
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to František Tureček.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Polášek, M., Tureček, F. Protonation sites in methyl nitrate and the formation of transient CH4NO3 radicals. A neutralization—reionization mass spectrometric and computational study. J Am Soc Mass Spectrom 11, 380–392 (2000). https://doi.org/10.1016/S1044-0305(00)00106-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1016/S1044-0305(00)00106-9

Keywords

Search

Navigation