Supplementary material for
Effect of CH Stretching Excitation on the Reaction
Dynamics of F + CHD3 → DF + CHD2
Jiayue Yang,1,a) Dong Zhang,1,a) Zhen Chen1), Florian Blauert,2,b) Bo
Jiang,1 Dongxu Dai,1,3) Guorong Wu,1,3,c) Donghui Zhang,1,3) and
Xueming Yang1,3,c)
1
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical
Physics, 457 Zhongshan Road, Dalian, Liaoning 116023, P. R. China
2
Dynamics at Surfaces, Faculty of Chemistry, Georg-August-Universität Göttingen,
37077 Göttingen, Germany
3
Synergetic Innovation Center of Quantum Information & Quantum Physics,
University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
a
These authors contributed equally to this work.
b
Present Address: Chair of Water Chemistry and Water Technology, Karlsruhe Institute of Technology, EnglerBunte-Ring 1, 76131 Karlsruhe, Germany.
c Authors to whom correspondence should be addressed.
Electronic mails: wugr@dicp.ac.cn (G. W.), xmyang@dicp.ac.cn (X. Y.)
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Images of the CHD2 (11, 1141, 1142 and 1143) products
The 111 , 111 411 , 111 402 and 111 413 vibronic bands were observed in the REMPI
spectrum for the excited-state reaction, indicating the generation of the 11 , 11 41 ,
11 42 , and 11 43 vibrational states of the CHD2 products in the excited-state reaction.
Underneath the peak of these vibronic bands, important contributions from the
neighboring 4𝑛𝑚 bands present. The IR-on and off images were taken with the REMPI
laser wavelength fixed at the peak of these vibronic bands. The IR-on images contain
contributions from both excited- and ground-state reactions, while the IR-off images
represent the latter. By scaling the IR-off images with the fraction of the excited-state
CHD3 reagents in the crossed-beam region and subtracting them from the respective
IR-on images, the images corresponding to the 11 , 11 41 , 11 42 , and 11 43 vibrational
states of the CHD2 products are derived, as shown in Figure S1. Two images are derived
for the 11 41 vibrational state of the CHD2 products, corresponding to the two peaks
of the 111 411 vibronic band, respectively.
Comparison of the product translational energy and angular distributions
between the excited- and ground-state reactions
The product translational energy and angular distributions are derived by integrating
the images over the scattering angle or along the radial direction, after the density-toflux correction.1 In Figure S2, the translational energy and angular distributions of the
CHD2(11) and CHD2(1142) products from the excited-state reaction are shown. In the
ground-state reaction, the corresponding vibrational states of the CHD2 products are
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CHD2(=0) and CHD2(4=2), respectively. The translational energy and angular
distributions of these two vibrational states from the ground-state reaction are also
included in Figure S2 for a close comparison. From Figure S2, it is clear that the product
translational energy and angular distributions remain largely unchanged in the excitedstate reaction when the excited CH bond is retained, comparing to the corresponding
vibrational states from the ground-state reaction. However, subtle differences between
the ground- and excited-state reactions are also presented, especially in the angular
distributions: The forward scattered products are heavily suppressed for the CHD2(1142)
channel and to a lesser extent for the CHD2(11) channel, suggesting that the excited CH
bond doesn’t totally act as a spectator when a D-atom is abstracted in the excited-state
reaction.
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Figure S1. Images of the CHD2 products of the 1141 (a and b), 1142 (c), 1143 (d) and 11
(e) vibrational states from the excited-state reaction. Images (a) and (b) were taken at
the peak of A and B in the REMPI spectra, respectively.
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Figure S2. Comparisons of translational energy and angular distributions of the CHD2
products between the ground- and excited-state reactions. The translational energy
distributions are scaled to a same maximum, and the angular distributions are scaled to
a same integral cross section. Black and red lines represent results from the groundstate and excited-state reaction respectively.
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Reference
S1. J. J. Lin, J. Zhou, W. Shiu, and K. Liu, Rev. Sci. Instrum. 74, 2495 (2003).
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