molecules undergoing extreme rotation. figure 2. angular distribution of the main fragments observed...
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Molecules undergoing extreme rotation
Figure 2. Angular distribution of the main fragments observed in the Multi Electron Dissociative Ionization (MEDI) of CO
PRL 82, 3420 (1999)
PRL 85, 542 (2000)
JCP 116, 10636 (2002)
Rotational Energy Level Clusters
1972 Dorney and Watson CH4 8-fold and 6-fold clusters
1978 Zhilinskii and Pavlichenkov H2O 4-fold clusters (Erb)
1978 Harter and Patterson Rotational energy surfaces and clusters
1991 Lehmann Local mode theory and clusters
1992 Kozin et al H2Se 4-fold clusters observed
1993 Kozin and Jensen H2Se 4-fold cluster theory (Erbs)
1994 Jensen and Bunker H2X 4-fold cluster symmetry
1996 Kozin et al H2Te 4-fold clusters (exp and theory)
1997 Jensen et al Review paper on 4-fold clusters
2000 Jensen Review paper on LMT and clusters
Emphasis is put on explaining the intimate relationship between local mode vibrations and the formation of both vibrational and rovibrational energy level clusters.
H2Te Rigid Rotor Energy Levels [E(JKaKc)-E(JJ0)]
JJ,0
JJ,1JJ-1,1
JJ-1,2
JJ-2,2
JJ-2,3
JJ-3,3
JJ-3,4
JJ-4,4
JJ,0JJ,1
JJ-1,1
JJ-1,2
J
Ae=6.26, Be=6.11, Ce=3.09 cm-1
4
4
Actual H2Te Energy Levels [E(JKaKc)-E(JJ0)]
J
JJ,0JJ,1JJ-1,1
JJ-1,2
JJ,0
JJ,1JJ-1,1
JJ-1,2
JJ-2,2
JJ-2,3
JJ-3,3
JJ-3,4
JJ-4,4
1R 1L
2L2R
1
2
1
11
22
2
JJ,0JJ,1JJ-1,1
JJ-1,2
in C2v(M)
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 2R 2L
J even J odd
A1 B2
B1 A2
A2 B1
B2 A1
1R 1L
2L2R
2
11
11
2
2 2
WHAT ARE THE LIFETIMES OF SUCH “DYNAMICALLY” CHIRAL STATES
at t=0
at time t
Using
2
Probability of being in |1R> at time t is:
For high J: ∆J i.e.
(Half-life)
Time for probability to have decreased to 1/2
∆J as function of J∆J
Zhilinskiiand
Pavlichenkov
Half-life as function of J
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