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Formation of interstellar HCCCCC via reaction of ground state carbon atom and diacetylene, HCCCCH
B. J. Sun1, C. Y. Huang1, H. H. Kuo1, K. T. Chen1, H. L. Sun1,C. H. Huang1, M. F. Tsai1, C. H. Kao1, Y. S. Wang1, L. G. Gao1, R. I. Kaiser2, A. H. H. Chang1
(1)Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien 974, Taiwan
(2)Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822, U. S. A.
• Why C(3P) + HCCCCH ? --carbon chain molecules ubiquitous in interstellar medium
--CnH ( n=1-8 ) detected
--C(3P), everywhere in interstellar clouds
--C(3P) + C2H2 C3H + H, studied intensively
--second member of C(3P) + HC2nH HC2n+1H C2n+1H + H
• What do we know ? -- mechanism: fast, barrierless C addition to πsystems
multiple collision complexes
isomerizations, dissociations
• What would we like to achieve ? with a rigorous theoretical investigation based on first principle,
to obtain reaction paths, rate constants, reaction mechanism,
intermediate lifetimes, product yield
• Difficulty : barrierless reaction with multiple collision complexes:
reaction rate of forming each collision complex?
e.g.
• How ?
Strategy
Capturing cross-sections (σcap's) of forming all collision complexes
Ab initio calculations on triplet HC5H ground state surface
Unimolecular rate constants
Solve rate equations
Product yields
Reaction paths for each collision complex
Most probable paths (reaction mechanism)
Theoretical methods
• Ab initio electronic structure calculation for reaction paths B3LYP/6-311G(d,p) optimized geometry, harmonic frequencies CCSD(T)/cc-pVTZ energy
• RRKM and variational RRKM rate constant -- For reaction , where A*: energized reactant : transition state P : product RRKM rate constant: where : symmetry factor : number of state of : density of state of A*
-- For barrierless reactions, ie. simple bond breaking reaction : variational RRKM, the geometry where is the transition state
PAA k *
A
)(
)()(
E
EEW
hEk
W
A
0
R
W
A
AP
A
P
A
• Capturing cross-section σcap
-- For long-range intermolecular potential of a bimolecular reaction, A+B P :
, where R : distance between centers of mass of two reactants: A - B R
------ Langevin model
-- now there are 3 collision complexes:
• Solve rate equations concentation evolutions product yields
31
31
or , )4
(3)( CE
CE capcap
methods
6)(R
CRV
31
3
31
2
31
1
3363
33
2262
22
1161
11
)3(
)2(
)1(
complex collision forming of coordinate reaction: , )3(
)(
complex collision forming of coordinate reaction: , )2(
)(
complex collision forming of coordinate reaction: , )1(
)(
C
C
C
CRR
CRV
CRR
CRV
CRR
CRV
c
c
c
C(3P) + HCCCCH 3 collision complexes
C1 paths and the most probable paths
C(3P) + HCCCCH
C(3P) + HCCCCH
C2 paths and the most probable paths
C(3P) + HCCCCH
C3 paths and the most probable paths
reaction mechanism ( most probable paths )
C(3P) + HCCCCH
C1 rate equations based on reaction mechanism:
]4[]1[
]3[]11[]3[
]11)[(]4[]11[
]4)[(]11[]1[]4[
]2[]3[]1[]2[
]1)[(]2[]4[]1[
10
615
151414
10114141
262
1221
ikdt
pd
ikikdt
id
ikkikdt
id
ikkkikckdt
id
ckikckdt
cd
ckkckikdt
cd
C1 evolution
C2 evolution
C3 evolution
product yield :
(C5H) + HC +
C(3P) + HCCCCH
summary
• C(3P) + HCCCCH reactions have been investigated theoretically by combining ab initio calculation, RRKM and variational RRKM theory, and Langevin model.
• Reaction paths, rate constants, most probable paths (reaction mechanisms), intermediate lifetimes, and product yield are predicted.
• 38 C5H2 isomers identified (32 newly found), HC5H crucial
10 C5H (2 new).
• The barrierless and exoergic C(3P) + HCCCCH reaction is an efficient route for diacetylene depletion and HCCCCC formation in interstellar medium.
acknowledgements
黃建瑜 , 孫秉键 , 孔憲和 , 陳寬澤 , 高志豪 , 黃瓊惠 , 蔡閔豐 , 王奕翔 , 高立均 , 孫慧倫
NSC, NCHC, National Dong Hwa University