Supplementary Material
Imaging the O(1D)+CD4→OD+CD3 Reaction Dynamics:
Internally Excited CD3 Products
Quan Shuai (帅全), Huilin Pan (潘慧琳), Jiayue Yang (杨家岳), Dong Zhang (张
冬), Bo Jiang (姜波), Dongxu Dai (戴东旭) and Xueming Yang (杨学明)a)
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, P. R. China
This supplementary material includes three parts of information:
1. REMPI spectroscopy of CD3 product from the O(1D)+CD4→OD+CD3 reaction we
obtained in the experiment. (Fig. S1)
2. Sliced velocity map ion images for the CD3 product at the v2=1,2 level at the collision
energy of 1.6, 2.8, and 6.8 kcal/mol. (Fig. S2)
3. Separated flux-velocity contour maps from insertion and abstraction pathways at the
collision energy of 1.6, 2.8, and 6.8 kcal/mol. (Fig. S3, S4)
a)
To whom all correspondence should be addressed. E-mail: xmyang@dicp.ac.cn
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Fig. S1 shows the (2+1) REMPI spectrum of the CD3 product from the O(1D)+CD4 reaction
at the collision energy of 6.8 kcal/mol via the 3p Rydberg state. The assignment of the
REMPI spectrum of the CD3 radical was made according to the previous work of Liu and
co-workers.1 From the REMPI spectrum, the CD3 product is only excited in the umbrella
mode. Vibrationally excited states up to v2=3 in the umbrella mode are populated in the CD3
product from the O(1D)+CD4 reaction. Unfortunately, the image of the v2=3 products (not
shown) shows no clear structure. This may be due to the overlapping of different rotationally
excited CD3 products on the REMPI spectra of v2=3 band. Consequently, the rotationally hot
CD3 products are detected at the same time as the rotationally cold CD3 products. Because of
the different velocity distributions of these products, the final images become ambiguous. In
this case, the images of the v2=3 products are difficult to analyse, so we only discuss the v2=0,
1, 2 products of CD3.
Fig. S2 depicts raw images for the CD3 product at the v2=1,2 level at the collision energy of
1.6, 2.8, and 6.8 kcal/mol, while separated flux-velocity contour maps from insertion and
abstraction pathways are given in Fig. S3, S4.
1
B. Zhang, J. Zhang, and K. Liu, J. Chem. Phys. 122, 104310 (2005).
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FIG. S1. Product CD3 radical (2+1) REMPI spectroscopy via the 3p2A″2 Rydberg state at the collision
energy of 6.8 kcal/mol. The whole spectrum exhibits several peaks which could be assigned to different
umbrella mode vibrational branches of the X2A″2→→3pz2A″2 transition. The inset shows the strong Q(000 )
branch around 59900 cm-1 and several weak peaks assigned to O, P, R, S branches.1 The rotationally
selected transition (K=0) of the Q(000 ) branch (not resolved on the spectrum) is labeled as N on the top, in
order to estimate the rotational state distribution of the CD3 products. The peak designated by an asterisk
(*) is assigned to the Q-branch of the 111 band.
1
Q. Shuai, H. Pan, J. Yang, D. Zhang, B. Jiang, D. Dai, and X. Yang, J. Phys. Chem. Lett. 3, 1310 (2012).
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FIG. S2. Raw images of product CD3(v2=1) at the collision energy of (A) 1.6, (C) 2.8, and (E) 6.8
kcal/mol. (B), (D), and (F) are taken at the same collision energies but for CD3(v2=2).
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FIG. S3. Flux-velocity contour maps of product CD3(v2=1) from insertion and abstraction pathways at the
collision energy of (A) 1.6, (B) 2.8, and (C) 6.8 kcal/mol.
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FIG. S4. As Fig. S3, except for the CD3(v2=2) product state.
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