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FIFTY YEARS IN ION CHEMISTRY WITH COLLEAGUES AND FRIENDS ZDENEK HERMAN V.Čermák Laboratory, J. Heyrovský Institute of Physical Chemistry, Academy of Sciences,

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Presentation on theme: "FIFTY YEARS IN ION CHEMISTRY WITH COLLEAGUES AND FRIENDS ZDENEK HERMAN V.Čermák Laboratory, J. Heyrovský Institute of Physical Chemistry, Academy of Sciences,"— Presentation transcript:

1 FIFTY YEARS IN ION CHEMISTRY WITH COLLEAGUES AND FRIENDS ZDENEK HERMAN V.Čermák Laboratory, J. Heyrovský Institute of Physical Chemistry, Academy of Sciences, Prague Gordon Research Conference “Gaseous Ions”, Galveston, Keynote Lecture,, March 5, 2009

2 (Mann et al 1940) - Talroze Stevenson, Schissler – Field, Franklin, Lampe 1957 THE FIRST TRY (July 30, 1958) INSTITUTE OF PHYSICAL CHEMISTRY, ACADEMY OF SCIENCES, PRAGUE

3 REACTIONS OF ELECTRONICALLY EXCITED REACTANT IONS ( in N 2, O 2, CO, CO 2, COS, CS 2 ) A.E. =21.7 eV N 2 + *( 4 Σ u ) + N 2 ( 1 Σ g + ) → N 3 + ( 3 Σ g - ) + N( 4 S) very small apparent cross section A.E.(N 3 + ) higher than IE(N 2 ) reaction endothermic with g.s. reactants exothermic only with electronically excited N 2 + * N 2 + *( 4 Σ u ) – theoretically predicted but not yet detected V. Čermák, Z. Herman, J. Chim. Phys., 1960 Vladimír Čermák

4 ASSOCIATIVE AND PENNING IONIZATION Kinetics of reactions in mixtures with metal vapors: Hg, Li, Na, K, Cs Ion-molecule reactions Associative ionization (excited neutral + A,M) Ar* m + Hg → ArHg + + e He* m + Li → HeLi + + e Kr* m + Cs → KrCs + + e Ar* m + C 2 H 2 → ArC 2 H e ION SOURCE WITH MOLECULAR BEAMS Penning ionization R* m + ABC→ R + ABC + + e → R + AB + + C + e → R + A + + BC + e mass spectra of product ions deposition of energy from R* m Penning ionization electron spectroscopy (V. Čermák) precise measurements of the energy of released electron C3H8C3H8

5 DYNAMICS OF ION-MOLECULE REACTIONS YALE 1964 – 65 (Richard Wolfgang) construction of EVA I (crossed-beam scattering machine) Reactive scattering of neutrals in beams ( ) [S.Datz, E.H Taylor (1955)] - D.R. Herschbach et al. – E.F. Green, J. Ross – R.B. Bernstein

6 C 2 H C 2 H 4 → [C 4 H 8 + ] → C 3 H CH 3 DYNAMICS OF ION-MOLECULE REACTIONS DISTINGUISHING COLLISION MECHANISMS BY SCATTERING New Haven, Boulder DIRECT MECHANISM (STRIPPING) even at quasi-thermal energies polarization stripping INTERMEDIATE COMPLEX FORMATION angular scattering translational energy distribution lifetime of complexes B. Mahan – A. Henglein - Champion, Doverspike

7 THE COMPLEX MINUET (to which Dudley Herschbach wrote the tune) SPECTATOR STRIPPING REACTION MECHANISMS

8 DYNAMICS OF ION-MOLECULE PROCESSES Prague, after 1969 EVA II (with V. Pacák)

9 H 2 + (v) + He → HeH + + H Experiments: V. Pacak, Z. Herman, K. Birkinshaw (Prague) Trajectory calculations: F. Schneider, U. Havemann, L. Zülicke (Berlin) ANGULAR TRANSLATIONAL VIBR ROT OVERALL ENERGY F.Schneider, U. Havemann, L. Zulicke, V. Pacak, K. Birkinshaw, Z. Herman, Chem.Phys.Lett. 37 (1976) 323 DYNAMICS OF ION-MOLECULE PROCESSES

10 Ar + + H 2 → Ar + H 2 + CHARGE TRANSFER H + - transfer complex H-atom transfer CH CH 4 → CH CH 3 PARALLEL MECHANISMS DYNAMICS OF ION-MOLECULE PROCESSES V. Pacák - K. Birkinshaw – A. Yencha – J. Futrell – P. Hierl – M. Henchman – B. Friedrich – J. Vančura

11 DYNAMICS OF REACTIONS OF DICATIONS Ar 2+ ( 3 P ) + He He 2+ + NO → He +* ( 2 P) + NO + ( 1 Σ +, v) 13 CO CO  13 CO + (B 2 Σ + ) + 12 CO + (A 2 Π) 13 CO + (A 2 Π) + 12 CO + (B 2 Σ + ) CHEMICAL REACTIONS CF D 2 → CF D 2 + → CF 2 D + + D + PRODUCT LUMINESCENCE CHRISTOPH OTTINGER Collaboration: B. Friedrich, J. Vančura, M. Sadílek, Z. Dolejšek, M. Fárník, L. Mrázek, J. Žabka, J. Roithová

12 ION - SURFACE COLLISIONS ENERGY PARTITIONING ION SURVIVAL IN SURFACE COLLISIONS SURFACE COLLISIONS OF CLUSTER IONS INNSBRUCK ( ) collaboration with Tilmann Märk et al. CH/C(HOPG) log S a = a – b (IE)

13 COLLEAGUESANDFRIENDS personal pages - ZH

14 Farewell to Mike Menzinger 1969 (Mike Menzinger, Jim Kerstetter, Jim Richardson, John Krenos, Pete Hierl, Rod LeRoy, Dick Wolfgang, John Hawke, Andy Yencha, Zdenek Herman, Al Lee, Cal Blakely)

15 BOULDER JILA A.D. 1980

16 JILA 1980: Carl Lineberger holding the reins JILA 1980: Beards and hairs of Steve Leone’s group.

17 JILA 1980: The FAIR (flowing-afterglow infra-red) people: Barney Ellison, Mark Smith, Tim Zwier, Jim Weisshaar, Veronica Bierbaum, Zdenek Herman

18 CU – Chemistry 1980: Eldon Ferguson watching the flow-tube centers CU – Chemistry 1980: Will Castleman

19 CU – Chemistry 1980: Chuck DePuy CU – Chemistry 1980: Barney Ellison

20 Dudley Herschbach (Harvard) in the center of mass Yuan T. Lee A.D (Berkeley and Taipei) U.S.A.

21 Steve Berry, Chicago Ugo Fano, Chicago

22 The Research Director (Graham Cooks)

23 Mike Henchman, Brandeis Jean Futrell at SASP 04

24 Peter Toennies (Göttingen) and Giorgio Benedek (Milano) struggling with the surface lattice dynamics GÖTTINGEN

25 Christoph Ottinger, Göttingen

26 Jürgen Troe (Göttingen) Evgenii Nikitin (Moscow, Haifa)

27 Tilmann Märk Werner Lindinger INNSBRUCK

28 OKAZAKI Saburo Nagakura Hiroki Nakamura Inosuke Koyano Tamotsu Kondow

29 EUROPEAN NETWORKS SRMIon Network: Paul-Marie Guyon, Orsay MCINet: Davide Bassi and Paolo Tosi, Trento

30 Dieter Gerlich, ChemnitzOdile Dutuit, Orsay

31 Diethard Böhme, TorontoHelmut Schwarz, Berlin

32 Franco Gian-Turco (Rome) Victor Sidis, Orsay The two Gentlemen of Madrid: Gerardo Delgado-Barrio and Pablo Villarreal MOLEC PEOPLE Enzo Aquilanti, Perugia

33 GORDON RESEARCH CONFERENCE, 1964


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