Combined theoretical and experimental study of the triple ionization of allene (C₃H₄) to quadruplet electronic states of C₃H₄³⁺

Abstract

Triple-charge-transfer (TCT) spectrometry was used to study the triple ionization of allene (C₃H₄). Ten clearly defined peaks were observed in the spectra, from which triple-ionization energies to electronic states of C₃H₄³⁺ were determined. Triple-ionization energies to quadruplet states were calculated using the ADC(2) Green's function method. The calculated values agree well with those measured, thus giving an insight into the electronic transitions which gave rise to the spectral peaks. Quadruplet states were considered since these will be populated if spin is conserved in the triple-electron-capture reactions on which TCT spectrometry is based.

References

1. N. Jeffreys, I. W. Griffiths, D. E. Parry and F. M. Harris, Chem. Phys. Lett., 1997, 266, 537.
2. A. S. Newton, J. Chem. Phys., 1964, 40, 607.
3. S. R. Andrews and D. E. Parry, Chem. Phys. Lett., 1992, 196, 630.
4. J. C. Slater and K. H. Johnson, Phys. Rev. B, 1972, 5, 844.
5. A. Tarantelli and L. S. Cederbaum, Phys. Rev. A, 1992, 46, 81.
6. F. M. Harris, I. W. Griffiths and A. R. Lee, Int. J. Mass. Spectrom. Ion Processes, 1996, 153, 57.
7. I. W. Griffiths, N. Jeffreys, A. R. Lee and F. M. Harris, Rapid Commun. Mass Spectrom., 1996, 10, 527.
8. N. Jeffreys, I. W. Griffiths, D. E. Parry and F. M. Harris, Int. J. Mass Spectrom. Ion Processes, 1997, 164, 133.
9. R. G. Kingston, M. Guilhaus, A. G. Brenton and J. H. Beynon, Org. Mass Spectrom., 1985, 20, 406.
10. S. R. Andrews, D. E. Parry, M. Vairamani and F. M. Harris, J. Chem. Soc., Faraday Trans., 1992, 88, 3403.
11. S. R. Andrews, D. E. Parry and F. M. Harris, J. Chem. Soc., Faraday Trans., 1995, 91, 1181.
12. D. E. Parry, Chem. Phys. Lett., 1997, 272, 148.
13. M. J. Frish, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Latham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, C. Y. Peng, P. U. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, GAUSSIAN94, Revision B.3, Gaussian, Inc., Pittsburgh, PA, 1995.
14. A. G. Maki and R. A. Toth, J. Mol. Spectrosc., 1965, 17, 136.
15. R. Krishnan, J. S. Binkley, R. Seeger and J. A. Pople, J. Chem. Phys., 1980, 72, 650.
16. N. Jeffreys, S. R. Andrews, D. E. Parry and F. M. Harris, Rapid Commun. Mass Spectrom., 1996, 10, 1693.
17. C. Moore, Atomic Energy Levels, NSRDS-NBS Circular No. 467, US GPO, Washington, 1949.