Ying Guo, Xibin Gu, Fangtong Zhang, Ralf I. Kaiser Department of Chemistry University of Hawai’i
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Transcript of Ying Guo, Xibin Gu, Fangtong Zhang, Ralf I. Kaiser Department of Chemistry University of Hawai’i
Ying Guo, Xibin Gu, Fangtong Zhang, Ralf I. KaiserDepartment of Chemistry
University of Hawai’iHonolulu, HI 96822
[email protected]://www.chem.hawaii.edu/Bil301/welcome.html
Reaction Dynamics in the C(3P) + C2H2(X1g
+) System
Introduction
c-C3H(X2B2) l-C3H(X2)
Science, 274, 1508 (1996)
8.8, 28, 45 kJmol-1
Introduction
l-C3(X1g+) + H2(X1g
+) RG = - 124 kJmol-1
- 100
- 200
- 300
- 400
H
CC
C
H
-137 (-130)
-215 (-205)
-253 (-246)
-388 (-382)
HCC
C
H C C CH
H
HC C C
H
- 2 (-0.2)- 8 (-0.6)
- 124
- 42c-C3H + H
l-C3H + H
c-C3 + H2
l-C3 + H2
(Bowman et al. JCP 125 081101 (2006))
Ochsenfeld et al. JCP 106 4141 (1997)
(-128)
(-129)
C
C
C
H H
(-124)
(-12)
(-66)(-80)
(41) (31)
(-127)
C(3P) + C2H2
Mebel et al. CPL 360, 139 (2002)
rela
tive
ener
gy, k
Jmol
-1
Introduction
l-C3(X1g+) + H2(X1g
+)
Faraday Discussions 119, 27 (2001)Faraday Discussions 119, 51 (2001)
Mebel et al. JACS 120, 5751 (1998) C3 formation via ISC
- 100
- 200
- 300
- 400
H
CC
C
H
-137 (-130)
-215 (-205)
-253 (-246)
-388 (-382)
HCC
C
H C C CH
H
HC C C
H
- 2 (-0.2)- 8 (-0.6)
- 124
- 42c-C3H + H
l-C3H + H
c-C3 + H2
l-C3 + H2
(-128)
(-129)
C
C
C
H H
(-124)
(-12)
(-66)(-80)
(41) (31)
(-127)
C(3P) + C2H2
- 500H
CC
C
H
(-454)C C C
H
H
(-404)H C C C
H
(-362)
(-201)
(-64)
(-185)
(-25)(-10)
HC C C
HH
CC
C
H
ISC
Introductionre
lativ
e en
ergy
, kJm
ol-1
- 100
- 200
- 300
- 400
H
CC
C
H
-137 (-130)
-215 (-205)
-253 (-246)
-388 (-382)
HCC
C
H C C CH
H
HC C C
H
- 2 (-0.2)- 8 (-0.6)
- 124
- 42c-C3H + H
l-C3H + H
c-C3 + H2
l-C3 + H2
(-128)
(-129)
C
C
C
H H
(-124)
(-12)
(-66)(-80)
(41) (31)
(-127)
C(3P) + C2H2
- 500H
CC
C
H
(-454)C C C
H
H
(-404)H C C C
H
(-362)
(-201)
(-64)
(-185)
(-25)(-10)
HC C C
HH
CC
C
H
ISC
rela
tive
ener
gy, k
Jmol
-1
Open Questions
C2H2 9033 16.00.3 - -
C(3P)/Ne 106310 4.90.3 8.00.1 61.50.3
C(3P)/He 203725 4.90.2 20.40.4 43.80.4
C(3P)/He 258128 2.90.1 30.70.6 37.20.4
13C2H2 8905 16.00.3 - -
C(3P)/Ne 105721 5.00.3 8.00.2 63.00.6
C(3P)/He 195018 4.40.1 19.30.3 46.80.4
C(3P)/He 253739 3.30.1 30.40.9 39.30.6
C2D2 8905 16.00.3 - -
C(3P)/Ne 105912 4.90.3 8.00.1 63.00.4
C(3P)/He 197814 5.10.2 19.80.3 46.40.4
C(3P)/He 256637 3.30.1 31.00.8 39.00.6
C2HD 8905 16.00.3 - -
C(3P)/Ne 108010 5.10.3 8.10.1 61.70.4
C(3P)/He 197617 5.30.2 19.50.3 45.40.4
C(3P)/He 256645 3.20.2 30.61.0 38.00.7
beam vp, ms-1 S EC, kJmol-1 CM
3736
3938
3836
383736
m/z
- 100
- 200
- 300
- 400
H
CC
C
H
-137 (-130)
-215 (-205)
-388 (-382)
HCC
C
H
HC C C
H
- 2 (-0.2)- 8 (-0.6)
- 124
- 42c-C3H + H
l-C3H + H
c-C3 + H2
l-C3 + H2
(-128)
(-129)(-124)(-127)
C(3P) + C2H2
- 500H
CC
C
H
(-454)C C C
H
H
(-404)H C C C
H
(-362)
(-201)
(-64)
(-185)
(-25)(-10)
HC C C
HH
CC
C
H
ISC
HC C C
H
HC C C
HH
CC
C
H
ISC
TS(+150)
C C CH
H
C C CH
H
H C C CH
13
HC C C
D
- 100
- 200
- 300
- 400
H
CC
C
H
-137 (-130)
-215 (-205)
-388 (-382)
HCC
C
H
HC C C
H
- 2 (-0.2)- 8 (-0.6)
- 124
- 42c-C3H + H
l-C3H + H
c-C3 + H2
l-C3 + H2
(-128)
(-129)(-124)(-127)
C(3P) + C2H2
- 500H
CC
C
H
(-454)C C C
H
H
(-404)H C C C
H
(-362)
(-201)
(-64)
(-185)
(-25)(-10)
HC C C
HH
CC
C
H
ISC
HC C C
D
C(3P) + C2D2(X1g+)
c-C3D(X2B2) + D(2S) RG = - 2 kJmol-1
l-C3D(X2) + D(2S) RG = + 8 kJmol-1
l-C3(X1g+) + D2(X1g
+) RG = - 126 kJmol-1
c-C3(X3A2’) + D2(X1g
+) RG = - 43 kJmol-1
Ochsenfeld et al. JCP 106, 4141 (1997)Mebel et al. CPL 360, 139 (2002)
C2H2 9033 16.00.3 - -
C(3P)/Ne 106310 4.90.3 8.00.1 61.50.3
C(3P)/He 203725 4.90.2 20.40.4 43.80.4
C(3P)/He 258128 2.90.1 30.70.6 37.20.4
13C2H2 8905 16.00.3 - -
C(3P)/Ne 105721 5.00.3 8.00.2 63.00.6
C(3P)/He 195018 4.40.1 19.30.3 46.80.4
C(3P)/He 253739 3.30.1 30.40.9 39.30.6
C2D2 8905 16.00.3 - -
C(3P)/Ne 105912 4.90.3 8.00.1 63.00.4
C(3P)/He 197814 5.10.2 19.80.3 46.40.4
C(3P)/He 256637 3.30.1 31.00.8 39.00.6
C2HD 8905 16.00.3 - -
C(3P)/Ne 108010 5.10.3 8.10.1 61.70.4
C(3P)/He 197617 5.30.2 19.50.3 45.40.4
C(3P)/He 256645 3.20.2 30.61.0 38.00.7
beam vp, ms-1 S EC, kJmol-1 CM
3736
3938
3836
383736
m/z
Crossed Molecular Beams Setup
C(3P) + C2H2 (8 kJmol-1; m/z = 37)C3H
C4H
(usec)
C(3P) + C2H2 (8 kJmol-1; m/z = 36)C3H
C4H
C3(R)
C3(E)
(usec)
C(3P) + C2H2 (20.4 kJmol-1; m/z = 37)C3H
C4H
(usec)
C(3P) + C2H2 (20.4 kJmol-1; m/z = 36)C3H C4H C3H
C4H
C3(R)
C3(E)
(usec)
C(3P) + C2H2 (30.7 kJmol-1; m/z = 37)C3H
C4H
(usec)
C(3P) + C2H2 (30.7 kJmol-1; m/z = 36)C3H C4H C3H
C4H
C3(R)
C3(E)
(usec)
C(3P) + C2H2
m/z = 37 m/z = 36
C3H
C4H
C3(R)
C3(E)
C(3P) + 13C2H2
C(3P) + 13C2H2
m/z = 39 m/z = 38
C3H
C4H
C3(R)
l-C3(X1g+) + H2(X1g
+)
C(3P) + C2H2/13C2H2
C3H//13C2CHC(3P) H
13C2CC(3P) H2
C(3P) + C2H2/13C2H2
- 100
- 200
- 300
- 400
H
CC
C
H
-137 (-130)
-215 (-205)
-388 (-382)
HCC
C
H
HC C C
H
- 2 (-0.2)- 8 (-0.6)
- 124
- 42c-C3H + H
l-C3H + H
c-C3 + H2
l-C3 + H2
(-128)
(-129)(-124)(-127)
C(3P) + C2H2
- 500H
CC
C
H
(-454)C C C
H
H
(-404)H C C C
H
(-362)
(-201)
(-64)
(-185)
(-25)(-10)
HC C C
HH
CC
C
H
ISC
Summary
C2H2 9033 16.00.3 - -
C(3P)/Ne 106310 4.90.3 8.00.1 61.50.3
C(3P)/He 203725 4.90.2 20.40.4 43.80.4
C(3P)/He 258128 2.90.1 30.70.6 37.20.4
13C2H2 8905 16.00.3 - -
C(3P)/Ne 105721 5.00.3 8.00.2 63.00.6
C(3P)/He 195018 4.40.1 19.30.3 46.80.4
C(3P)/He 253739 3.30.1 30.40.9 39.30.6
C2D2 8905 16.00.3 - -
C(3P)/Ne 105912 4.90.3 8.00.1 63.00.4
C(3P)/He 197814 5.10.2 19.80.3 46.40.4
C(3P)/He 256637 3.30.1 31.00.8 39.00.6
C2HD 8905 16.00.3 - -
C(3P)/Ne 108010 5.10.3 8.10.1 61.70.4
C(3P)/He 197617 5.30.2 19.50.3 45.40.4
C(3P)/He 256645 3.20.2 30.61.0 38.00.7
beam vp, ms-1 S EC, kJmol-1 CM
3736
3938
3836
383736
m/z
Ionization Potentials of C3H Isomers
C2H2
C3H
Chemical Dynamics Beamline Advanced Light Source
L. Belau, S. Leone, M. Ahmed, R.I. Kaiser
10 20 30 40 50 60 70 80
0
5
10
15
20
2511 eV
7349
74
50
37
Ion
Inte
nsity
(cou
nts)
m/z
C3H
C4H
C4H2
C6H2
8.8 9.0 9.2 9.4 9.6 9.8 10.0
0
10
20
30 Experimental Mixture 52:48 Mixture 100:0 Mixture 0:100
Ioni
zatio
n ef
ficie
ncy
(cou
nts)
Photon energy (eV)
B. Braams J. Bowman
Ionization Potentials
IP(l-C3H) = 9.06 eV
IP(c-C3H) = 9.66 eV
0.1 eV
Experiments*
IP(l-C3H) = 9.1 eV
IP(c-C3H) = 9.6 eV
0.1 eV
*L. Belau S. Leone M. Ahmed R.I. Kaiser
Acknowledgements
Y. Guo, F. Zhang, X. Gu
L. Belau S. Leone
M. Ahmed
B. Braams J. Bowman