Abstract
The relative collision cross sections σ c of selected precursor ions that collide with helium at high ion kinetic energies (kiloelectronvolts) have been obtained by monitoring the ion beam attenuation at different collision pressures. A value for the total collision cross section is obtained, which includes contributions from different processes that lead to fragmentation, scattering, charge exchange, charge inversion, and stripping. For n-alkanes and n-alkylbenzenes the σ c value increases linearly by 0.1 per methylene group. Linear relationships exist between relative collision cross section and ionization cross section σ i, and polarizability α of the corresponding neutral molecule, but different equations are required for the description of σ c in each chemical series. A simple relationship, which requires only the chemical formula of the precursor ion, has been determined that can predict all relative collision cross sections with an average error of 3.5%. The total relative collision cross section increases with the size of the ion. The experimental results are in agreement with the predictions of the hard-sphere collision theory. The approach can be applied to determine the relative collision cross sections at different ion kinetic energy regimes and collisions with different target gases.
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Allgood, C.; Orlando, R.; Munson, B. J. Am. Soc. Mass. Spectrom. 1990, 1, 397.
Bartmess, J. E.; Georgiadis, R. M. Vacuum 1983, 33, 149.
Laramee, J. A.; Cameron, D.; Cooks, R. G. J. Am. Chem. Soc. 1981, 103, 12.
van Tilborg, M. W. E. M.; van Thuijl, J. Org. Mass Spectrom. 1984, 19, 217.
van Houte, J. J.; de Koster, C. G.; van Thuijl, J. Int. J. Mass. Spectrom. Ion Processes 1992, 115, 173.
Todd, P. J.; McLafferty, F. W. Int. J. Mass Spectrom. Ion Phys. 1981, 38, 371.
Fitch, W. L.; Sauter, A. D. Anal. Chem. 1983, 55, 832.
Gioumousis, G.; Stevenson, D. P. J. Chem. Phys. 1958, 29, 294.
Field, F. H.; Franklin, J. L.; Lampe, F. W. J. Am. Chem. Soc. 1957, 79, 2419.
Su, T.; Bowers, M. T. J. Chem. Phys. 1973, 58, 3027.
Su, T.; Su, E. C. F.; Bowers, M. T. J. Chem. Phys. 1978, 69, 2243.
Miller, K. J.; Savchik, J. A. J. Am. Chem. Soc. 1979, 101, 7206.
Harrison, A. G.; Jones, E. G.; Gupta, S. K.; Nagy, G. P. Can. J. Chem. 1966, 44, 1967.
Beran, J. A.; Kevan, L. J. Phys. Chem. 1969, 73, 3866.
Levine, R. D.; Bernstein, R. B. Molecular Reaction Dynamics and Chemical Reactivity; Oxford University Press: New York, 1987; p 26.
Bondi, A. J. Phys. Chem. 1964, 68, 441.
Holmes, J. L. Org. Mass Spectrom. 1985, 20, 169.
van Houte, J. J.; van Thuijl, J. Int. J. Mass. Spectrom. Ion Processes 1994, 113, 121.
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Roussis, S.G. Relative collision cross sections of organic ions. J Am Soc Mass Spectrom 6, 803–811 (1995). https://doi.org/10.1016/1044-0305(95)00323-6
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DOI: https://doi.org/10.1016/1044-0305(95)00323-6