C-O Bond Dissociation and Induced Chemical Ionization Using High Energy (CO2)n+ Gas Cluster Ion Beam

  • Hua Tian
  • Dawid Maciążek
  • Zbigniew Postawa
  • Barbara J. Garrison
  • Nicholas Winograd
Research Article


A gas cluster ion beam (GCIB) source, consisting of CO2 clusters and operating with kinetic energies of up to 60 keV, has been developed for the high resolution and high sensitivity imaging of intact biomolecules. The CO2 molecule is an excellent molecule to employ in a GCIB source due to its relative stability and improved focusing capabilities, especially when compared to the conventionally employed Ar cluster source. Here we report on experiments aimed to examine the behavior of CO2 clusters as they impact a surface under a variety of conditions. Clusters of (CO2)n+ (n = 2000~10,000) with varying sizes and kinetic energies were employed to interrogate both an organic and inorganic surface. The results show that C-O bond dissociation did not occur when the energy per molecule is less than 5 eV/n, but that oxygen adducts were seen in increasing intensity as the energy is above 5 eV/n, particularly, drastic enhancement up to 100 times of oxygen adducts was observed on Au surface. For Irganox 1010, an organic surface, oxygen containing adducts were observed with moderate signal enhancement. Molecular dynamics computer simulations were employed to test the hypothesis that the C-O bond is broken at high values of eV/n. These calculations show that C-O bond dissociation occurs at eV/n values less than the C-O bond energy (8.3 eV) by interaction with surface topological features. In general, the experiments suggest that the projectiles containing oxygen can enhance the ionization efficiency of surface molecules via chemically induced processes, and that CO2 can be an effective cluster ion source for SIMS experiments.

Graphical Abstract


Gas cluster ion beam C-O bond dissociation Carbon dioxide cluster Irganox 1010 Au film Molecular dynamics computer simulations 



This work was supported by NIH grants 5R01GM113746-21. DM and ZP gratefully acknowledge financial support from the Polish National Science Centre, Grant No. 2015/19/B/ST4/01892. MD simulations were performed at the PLGrid Infrastructure.

Supplementary material

13361_2018_2102_MOESM1_ESM.docx (2 mb)
Supplementary Figure S1 (DOCX 2033 kb)


  1. 1.
    Tian, H., Sparvero, L.J., Amoscato, A.A., Bloom, A., Bayır, H., Kagan, V.E., et al.: Gas cluster ion beam time-of-flight secondary ion mass spectrometry high-resolution imaging of cardiolipin speciation in the brain: identification of molecular losses after traumatic injury. Anal. Chem. 89, 4611–4619 (2017)CrossRefGoogle Scholar
  2. 2.
    Rabbani, S., Barber, A.M., Fletcher, J.S., Lockyer, N.P., Vickerman, J.C.: TOF-SIMS with argon gas cluster ion beams: a comparison with C60+. Anal. Chem. 83, 3793–3800 (2011)CrossRefGoogle Scholar
  3. 3.
    Ninomiya, S., Nakata, Y., Ichiki, K., Seki, T., Aoki, T., Matsuo, J.: Measurements of secondary ions emitted from organic compounds bombarded with large gas cluster ions. Nucl. Instrum. Methods Phys. Res. B. 256, 493–496 (2007)CrossRefGoogle Scholar
  4. 4.
    Ninomiya, S., Ichiki, K., Yamada, H., Nakata, Y., Seki, T., Aoki, T., et al.: Precise and fast secondary ion mass spectrometry depth profiling of polymer materials with large Ar cluster ion beams. Rapid Commun. Mass Spectrom. 23, 1601–1606 (2009)CrossRefGoogle Scholar
  5. 5.
    Wucher, A., Tian, H., Winograd, N.: A mixed cluster ion beam to enhance the ionization efficiency in molecular secondary ion mass spectrometry. Rapid Commun. Mass Spectrom. 28, 396–400 (2014)CrossRefGoogle Scholar
  6. 6.
    Tian, H., Wucher, A., Winograd, N.: Reducing the matrix effect in organic cluster SIMS using dynamic reactive ionization. J. Am. Soc. Mass Spectrom. 27, 2014–2024 (2016)CrossRefGoogle Scholar
  7. 7.
    Tian, H., Wucher, A., Winograd, N.: Reduce the matrix effect in biological tissue imaging using dynamic reactive ionization and gas cluster ion beams. Biointerphases. 11, 02A320 (2016)CrossRefGoogle Scholar
  8. 8.
    Tian, H., Wucher, A., Winograd, N.: Dynamic reactive ionization with cluster secondary ion mass spectrometry. J. Am. Soc. Mass Spectrom. 27, 285–292 (2016)CrossRefGoogle Scholar
  9. 9.
    Tian, H., Maciazek, D., Postawa, Z., Garrison, B.J., Winograd, N.: CO2 cluster ion beam, an alternative projectile for secondary ion mass spectrometry. J. Am. Soc. Mass Spectrom. 27, 1476–1482 (2016)CrossRefGoogle Scholar
  10. 10.
    Akizuki, M., Matsuo, J., Yamada, I., Harada, M., Ogasawara, S., Doi, A.: SiO2 film formation at room temperature by gas cluster ion beam oxidation. Nucl. Instr. Meth. Phys. Res. Section B. 112, 83–85 (1996)CrossRefGoogle Scholar
  11. 11.
    Fletcher, J.S., Rabbani, S., Henderson, A., Blenkinsopp, P., Thompson, S.P., Lockyer, N.P., et al.: A new dynamic in mass spectral imaging of single biological cells. Anal. Chem. 80, 9058–9064 (2008)CrossRefGoogle Scholar
  12. 12.
    Garrison, B.J., Postawa, Z.: Computational view of surface based organic mass spectrometry. Mass Spectrom. Rev. 27, 289–315 (2008)CrossRefGoogle Scholar
  13. 13.
    Liu, L.C., Liu, Y., Zybin, S.V., Sun, H., Goddard, W.A.: ReaxFF-lg: correction of the ReaxFF reactive force field for London dispersion, with applications to the equations of state for energetic materials. J. Phys. Chem. A. 115, 11016–11022 (2011)CrossRefGoogle Scholar
  14. 14.
    Biersack, J.P.: The effect of high charge states on the stopping and ranges of ions in solids. Nucl. Instrum. Meth. B. 80-1, 12–15 (1993)CrossRefGoogle Scholar
  15. 15.
    Williams, P.L., Mishin, Y., Hamilton, J.C.: An embedded-atom potential for the Cu-Ag system. Model. Simul. Mater. Sci. Eng. 14, 817–833 (2006)CrossRefGoogle Scholar
  16. 16.
    Plimpton, S.: Fast parallel algorithms for short-range molecular-dynamics. J. Comput. Phys. 117, 1–19 (1995)CrossRefGoogle Scholar
  17. 17.
    Maciazek, D., Paruch, R.J., Postawa, Z., Garrison, B.J.: Micro- and macroscopic modeling of sputter depth profiling. J. Phys. Chem. C. 120, 25473–25480 (2016)CrossRefGoogle Scholar
  18. 18.
    Postawa, Z., Czerwinski, B., Szewczyk, M., Smiley, E.J., Winograd, N., Garrison, B.J.: Enhancement of sputtering yields due to C60 versus Ga bombardment of Ag{111} as explored by molecular dynamics simulations. Anal. Chem. 75, 4402–4407 (2003)CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 2018

Authors and Affiliations

  1. 1.Chemistry DepartmentThe Pennsylvania State UniversityUniversity ParkUSA
  2. 2.Smoluchowski Institute of PhysicsJagiellonian UniversityKrakowPoland

Personalised recommendations