Hyperthermal collisions of atomic clusters and fullerenes

doi:10.1016/j.ijms.2003.11.019

International Journal of Mass Spectrometry

Volume 233, Issues 1–3, 15 April 2004, Pages 1-12

Dedicated to T. D. Märk on the occasion of his 60th birthday.

https://doi.org/10.1016/j.ijms.2003.11.019 Get rights and content

Abstract

Among the many directions that mass spectrometry of atomic clusters and fullerenes have taken, analysis of their collisions with atoms, molecules, or surfaces has been particularly successful. We will first review experimental and theoretical work pertaining to hyperthermal collisions of charged or neutral clusters, including the formation of endohedral fullerenes. We will then present experimental data on the unimolecular formation of C₆₀⁺ and C₅₈⁺ from collisionally excited C₆₀. Based on recently proposed rate coefficients for dissociation and ionization of C₆₀ and C₅₈, we derive the efficiency of energy transfer, from translational to vibrational modes, for inelastic C₆₀+K⁺ collisions.

Section snippets

Dedication

Two decades ago, a competition ensued between Tilmann Märk’s cluster group at the University of Innsbruck and the cluster group at the University of Konstanz that included Ekkehard Recknagel and one of the authors, O.E. We were competing in two “hot” areas, namely characterization of fission reactions of metastable, multiply charged cluster, and formation of negatively charged clusters by electron attachent. In 1985, Tilmann spent a semester at the University of Konstanz where he taught nuclear

Experiment

Fig. 1 shows the experimental setup. A metal ion gun provides a beam of potassium ions that are generated by surface ionization. These ions have a small kinetic energy spread of about 2 k_BT≈0.3 eV [184]. We use cylindrical, resistively heated cartridges capped with a 0.25 in. diameter porous tungsten plug, coated with aluminasilicate glass which is doped with potassium [185]. The continuous beam of K⁺ emitted from the tungsten plug is accelerated, decelerated, and then chopped into bunches of 2 μs

Experimental results

In Fig. 2, we display the intensities of C₆₀⁺ and C₅₈⁺ ions (full and open circles, respectively), formed as a result of collisions of C₆₀ with K⁺ ions. The abscissa display the collision energy in the lab and the center-of-mass system. The lines show the result of our kinetic model as explained in the next section. The experimental C₆₀⁺ ion intensity peaks at E_cm≈48 eV, some 6 eV below the C₅₈⁺ ion. Qualitatively similar shifts between C₆₀⁺ and C₅₈⁺ have been observed under a variety of

Modeling the kinetics

In this section, we will assume that all empty fullerene ions observed in the experiment are formed as a result of inelastic, non-reactive collisions between K⁺ and C₆₀ (reaction 1a). The vibrationally excited $C_{60}^{∗}$ is, like any other neutral product, not observable, but it may lead to ion formation through a series of competing reaction channels:To model the kinetics, we need expressions for the dependence of the rate coefficients k_i (i=1–6) on the excess energy E^∗ of the parent ion of the

Discussion

The primary objective of the present work is to determine the relation between the collision energy in the center-of-mass system, E_cm, and the amount of energy, ΔE, that is converted from translational to vibrational modes in an inelastic collision between C₆₀ and K⁺ (reaction 1a). For a given set of parameters (primarily the frequency factors ν_i and the activation energies E_i in the Arrhenius relations, Eq. (4)), our model lets us predict the intensities of C₆₀⁺ and C₅₈⁺ as a function of ΔE.

Conclusion

We have analyzed the intensities of C₆₀⁺ and C₅₈⁺ ions that form after inelastic K⁺+C₆₀ collisions in the gas phase. The basic assumption is that all reactions are statistical, with full equilibration of the excitation energy. Although a large number of input parameters are required in the model that are not well known, we show that a set of values recently derived by Tomita et al. from a very different experiment [195] does lead to reasonable agreement between the model and experiment when

Acknowledgements

This material is based upon work supported by the National Science Foundation under Grant No. 9507959.

References (220)

M. Knapp et al.
Chem. Phys. Lett.
(1986)
H. Deutsch et al.
Int. J. Mass Spectrom.
(2000)
D.X. Zhang et al.
Int. J. Mass Spectrom.
(2000)
M. Kolibiar et al.
Chem. Phys. Lett.
(1994)
E.E.B. Campbell et al.
Chem. Phys.
(1998)
J.L. Gong et al.
Nucl. Instrum. Methods B
(1998)
R. Deng et al.
Chem. Phys. Lett.
(2002)
R. Deng et al.
Int. J. Mass Spectrom.
(2003)
Y.J. Basir et al.
Int. J. Mass Spectrom.
(1999)
G. Seifert et al.
Phys. Lett. A
(1994)

F.Z. Cui et al.

Phys. Lett. A

(1994)

K. Shiga et al.

Mater. Sci. Eng. A Struct. Mater. Prop. Microstruct. Process.

(2000)

H. Sprang et al.

Chem. Phys. Lett.

(1994)

J. Hrusak et al.

Chem. Phys. Lett.

(1992)

T. Aree et al.

Chem. Phys. Lett.

(1997)

E.E.B. Campbell et al.

J. Phys. Chem. Solids

(1997)

C. Brink et al.

Chem. Phys. Lett.

(1998)

R. Hettich et al.

Int. J. Mass Spectrom.

(1999)

D.C. Lorents et al.

Chem. Phys. Lett.

(1995)

T. Weiske et al.

Chem. Phys. Lett.

(1994)

F. Rohmund et al.

Chem. Phys. Lett.

(2000)

T. Braun et al.

Chem. Phys. Lett.

(1998)

C. Lifshitz

Int. J. Mass Spectrom.

(2000)

D. Kreisle, K. Leiter, O. Echt, T.D. Märk, in: F. Howorka, W. Lindinger, T.D. Märk (Eds.), 5th Symposium on Atomic and...

D. Kreisle et al.

Phys. Rev. Lett.

(1986)

D. Kreisle et al.

Z. Phys. D

(1986)

M. Knapp, O. Echt, D. Kreisle, T.D. Märk, E. Recknagel, in: P. Jena, B.K. Rao, S.N. Khanna, Physics and Chemistry of...

K. Leiter et al.

J. Phys. Chem.

(1987)

U. Buck et al.

J. Chem. Phys.

(1996)

T.A. Beu et al.

J. Chem. Phys.

(2002)

S. Grebenev et al.

Science

(2000)

F. Stienkemeier et al.

J. Chem. Phys.

(2001)

J.A. Northby

J. Chem. Phys.

(2001)

T.D. Märk, in: Linking the Gaseous and Condensed Phases of Matter: The Behavior of Slow Electrons (NATO ASI Series B,...

T.D. Märk, O. Echt, in: H. Haberland (Ed.), Clusters of Atoms and Molecules II, vol. 56, Springer-Verlag, Berlin, 1994,...

S. Matt et al.

J. Chem. Phys.

(2000)

G. Hanel et al.

Z. Phys. Chem. (Munich)

(2000)

S.L. Anderson, in: H. Haberland (Ed.), Clusters of Atoms and Molecules II, vol. 56, Springer-Verlag, Berlin, 1994, p....

S. Krückeberg et al.

J. Chem. Phys.

(2001)

P. Armentrout

Ann. Rev. Phys. Chem.

(2001)

K. Koszinowski, D. Schroder, H. Schwarz, R. Liyanage, P.B. Armentrout, J. Chem. Phys. 117 (2002)...

D. Vardhan et al.

J. Chem. Phys.

(2003)

C.D. Bradley et al.

J. Chem. Soc. Faraday Trans.

(1994)

M. Barat et al.

J. Chem. Phys.

(1999)

P.L.M. Plummer et al.

J. Chem. Phys.

(1987)

P.L.M. Plummer, T.S. Chen, in: P. Jena, B.K. Rao, S.N. Khanna (Eds.), Physics and Chemistry of Small Clusters (NATO ASI...

O. Knospe et al.

Phys. Rev. A

(2000)

E.E.B. Campbell et al.

Rep. Prog. Phys.

(2000)

D.K. Böhme, O.V. Boltalina, P. Hvelplund, in: L.M. Kadish, R.S. Ruoff Fullerenes, Wiley, New York, 2000, p....

F. Rohmund et al.

Phys. Rev. Lett.

(1996)

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¹: Present address: Department of Chemistry, University of Illinois at Chicago, Chicago, IL 60607-7061, USA.

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ReviewHyperthermal collisions of atomic clusters and fullerenes

Abstract

Section snippets

Dedication

Experiment

Experimental results

Modeling the kinetics

Discussion

Conclusion

Acknowledgements

Chem. Phys. Lett.

Int. J. Mass Spectrom.

Int. J. Mass Spectrom.

Chem. Phys. Lett.

Chem. Phys.

Nucl. Instrum. Methods B

Chem. Phys. Lett.

Int. J. Mass Spectrom.

Int. J. Mass Spectrom.

Phys. Lett. A

Phys. Lett. A

Mater. Sci. Eng. A Struct. Mater. Prop. Microstruct. Process.

Chem. Phys. Lett.

Chem. Phys. Lett.

Chem. Phys. Lett.

J. Phys. Chem. Solids

Chem. Phys. Lett.

Int. J. Mass Spectrom.

Chem. Phys. Lett.

Chem. Phys. Lett.

Chem. Phys. Lett.

Chem. Phys. Lett.

Int. J. Mass Spectrom.

Phys. Rev. Lett.

Z. Phys. D

J. Phys. Chem.

J. Chem. Phys.

J. Chem. Phys.

Science

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

Z. Phys. Chem. (Munich)

J. Chem. Phys.

Ann. Rev. Phys. Chem.

J. Chem. Phys.

J. Chem. Soc. Faraday Trans.

J. Chem. Phys.

J. Chem. Phys.

Phys. Rev. A

Rep. Prog. Phys.

Phys. Rev. Lett.

Review
Hyperthermal collisions of atomic clusters and fullerenes