Post on 15-Mar-2016
description
Ying Guo, Xibin Gu, Fangtong Zhang, Ralf I. KaiserDepartment of Chemistry
University of Hawai’iHonolulu, HI 96822
kaiser@gold.chem.hawaii.eduhttp://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