conformer selective and vibrationally mediated photodissociation dynamics of propanal cation lei...
TRANSCRIPT
![Page 1: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/1.jpg)
Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation
Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits
Department of Chemistry, Wayne State University
![Page 2: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/2.jpg)
Geometric optimization of propanal cation (C3H6O+)
cis conformer (0.07o) gauche conformer (118.9o)
Gauche form is more stable and energy difference is only about 65 cm-1 in the lowest ionic state with the barrier height, 344 cm-1.
Cis form is more stable in both the ground and Rydberg states of neutral propanal.
The geometry optimization was performed with B3LYP/6-311++G** by Gaussian 03.
![Page 3: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/3.jpg)
Two-photon spectroscopy of the 3s n Rydberg transition of propanal
J. Pfab, et al., J. Chem. Soc., Faraday Trans., 1997, 93, 2883
841 cm-1
![Page 4: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/4.jpg)
Photoionization of propanal by (2 + 1) REMPI
I.P=9.999 (0.003)
I.P=9.944
M. H. Kim, L. Shen, A. G. Suits, Phys. Chem. Chem. Phys. 8, 2933-2939 (2006)
![Page 5: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/5.jpg)
Photofragment (C3H5O+) images from the vibrationally and conformationally mediated photodissociation of propanal cation
cis origin (53943.9 cm-1) cis 151 (54146.0 cm-1) cis 152 (54349.6 cm-1) cis 153 (54554.8 cm-1)
gauche origin (54785.3 cm-1) cis 81 (55085.2 cm-1) cis 61 (55307.2 cm-1)cis 154 (54758.8 cm-1)
![Page 6: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/6.jpg)
Conformer specific photodissociation of propanal cation
Cis
Gauche
Total Translational Energy (eV)
![Page 7: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/7.jpg)
Potential energy diagram for C3H6O+
M. H. Kim, L. Shen, HL. Tao, T. J. Martinez, A. G. Suits. Science, 315, 1561-1565 (2007)
![Page 8: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/8.jpg)
Dynamics on the D2 state
AIMS (ab initio multiple spawning)
![Page 9: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/9.jpg)
Dynamics on the dark state (D1)
![Page 10: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/10.jpg)
Deuterated result
CH3CD2CHO+ CH3CD2CO+ + H
H loss:
CH3CDCDHO+ CH3CDCDO+ + H
D loss:
CH3CD2CHO+
CH3CDCDHO+ CH3CDCHO+ + D
HL. Tao, L. Shen, M. H. Kim, A. G. Suits, T. J. Martinez (in preparation)
![Page 11: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/11.jpg)
Reaction rates on the ground state
RRKM simulations:
![Page 12: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/12.jpg)
Dynamics on the ground state
MOLPRO CAS (5/5)-PT2/6-31G**
![Page 13: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/13.jpg)
Photofragment images (C3H5O+) with vibrational excitation
1123
1124
2223
2224
11
102315 1
1102415 1
1202315
11
202415
![Page 14: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/14.jpg)
Mode selective photodissociation dynamics
3.30 3.35 3.40 3.45 3.50 3.55 3.60 3.6510
15
20
25
30
35
40
45
61 0
91 0
101 0
71 0/111 0
81 0
ga
uch
e
152 02
32 2
152 02
42 2
154 0
151 02
32 21
52 0231 1
153 0
152 02
41 1
151 02
42 2
151 02
31 11
52 0
232 2
151 02
41 1242 2
231 1
151 0
241 1
cis
Ave
rag
e r
atio
(fa
st/
tota
l) %
Total available energy (eV)
![Page 15: Conformer selective and vibrationally mediated photodissociation dynamics of propanal cation Lei Shen, Myunghwa Kim, Bailin Zhang, Arthur G. Suits Department](https://reader035.vdocuments.mx/reader035/viewer/2022062620/5519bf4a550346047c8b45c8/html5/thumbnails/15.jpg)
Acknowledgements
Wayne State: Stanford:
Prof. Arthur G. Suits Prof. Todd J. Martinez
Hongli Tao
Prof. Myung Hwa Kim
Dr. Bailin Zhang