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Molecules undergoing extreme rotation. Figure 2. Angular distribution of the main fragments observed in the Multi Electron Dissociative Ionization (MEDI)

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Presentation on theme: "Molecules undergoing extreme rotation. Figure 2. Angular distribution of the main fragments observed in the Multi Electron Dissociative Ionization (MEDI)"— Presentation transcript:

1 Molecules undergoing extreme rotation

2 Figure 2. Angular distribution of the main fragments observed in the Multi Electron Dissociative Ionization (MEDI) of CO

3

4 PRL 82, 3420 (1999)

5 PRL 85, 542 (2000)

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7 JCP 116, 10636 (2002)

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9

10 Rotational Energy Level Clusters 1972 Dorney and WatsonCH 4 8-fold and 6-fold clusters 1978 Zhilinskii and PavlichenkovH 2 O 4-fold clusters (E rb ) 1978 Harter and Patterson Rotational energy surfaces and clusters 1991 LehmannLocal mode theory and clusters 1992 Kozin et alH 2 Se 4-fold clusters observed 1993 Kozin and JensenH 2 Se 4-fold cluster theory (E rbs ) 1994 Jensen and Bunker H 2 X 4-fold cluster symmetry 1996 Kozin et al H 2 Te 4-fold clusters (exp and theory) 1997 Jensen et al Review paper on 4-fold clusters 2000 Jensen Review paper on LMT and clusters

11 Emphasis is put on explaining the intimate relationship between local mode vibrations and the formation of both vibrational and rovibrational energy level clusters.

12 H 2 Te Rigid Rotor Energy Levels [E(J KaKc )-E(J J0 )] J J,0 J J,1 J J-1,1 J J-1,2 J J-2,2 J J-2,3 J J-3,3 J J-3,4 J J-4,4 J J,0 J J,1 J J-1,1 J J-1,2 J A e =6.26, B e =6.11, C e =3.09 cm -1 4 4

13 Actual H 2 Te Energy Levels [E(J KaKc )-E(J J0 )] J J J,0 J J,1 J J-1,1 J J-1,2 J J,0 J J,1 J J-1,1 J J-1,2 J J-2,2 J J-2,3 J J-3,3 J J-3,4 J J-4,4

14 1R 1L 2L 2R 1 2 1 1 1 2 2 2 J J,0 J J,1 J J-1,1 J J-1,2 in C 2v (M)

15 Kinetic Tunneling We can write For one form (12), E*, and (12)* are not feasible. “A dynamical barrier”. Thus the MS group is just {E} for each form and it must be chiral. 1L 1R 2R2L J evenJ odd A 1 B 2 B 1 A 2 A 2 B 1 B 2 A 1

16 1R 1L 2L 2R 2 1 1 1 1 2 22 WHAT ARE THE LIFETIMES OF SUCH “DYNAMICALLY” CHIRAL STATES

17 at t=0 at time t Using 2

18 Probability of being in |1R> at time t is: For high J: ∆J∆J i.e.

19 (Half-life) Time for probability to have decreased to 1/2

20 ∆ J as function of J ∆J∆J Zhilinskii and Pavlichenkov

21 Half-life as function of J

22 The prequel to and now for something completely different... IOP Publishing, Bristol, UK Expected publication date: December 2004, 380 pages, expected price 65 US$ http://bookmark.iop.org/bookpge.htm?&isbn=0750309415 (or see our homepages)

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