Quasiclassical dynamics for the H+HS abstraction and exchange
reactions on the 3A'' and the 3A' states
Zhi Xin Duan a, b, Wen Liang Li a, Wen Wu Xu a, Shuang Jiang Lv *a,
a
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China
b
Department of Physics, DaLian JiaoTong University, Dalian, 116028, China
Supplementary Information:
In this supplementary information, we firstly plot the comparison of the
QCT-GB (Gaussian binning) and QCT-HB (histogram binning) product
rotational state distributions in the reaction H + H′S(v=0, j=0) for v’=1-3 at
Ecol = 1.0 eV. In the calculations, a full-width-half-maximum for the
Gaussian functions of 0.1 is used for the GB weighting. From the Fig.S1,
one can see that the QCT-HB rotational state distributions are very similar to
the QCT-GB ones for the HS +H′ channel (bottom panel), implying the
binning procedure has only a small influence on the exchange reaction.
However, for the H2+S forming channel, the QCT-HB method are not
capable of reproducing the QCT-GB calculations, especially for products
into lower vibational states. In particular, for v’=0, the HB procedure leads to
cross section values which are lower than those from GB calculations,
whereas for v′=1, the HB method overestimates the GB results.
Secondly, we plot the product rovibational state distributions for
abstraction and exchange processes for the 3A' PES. The Gaussian binning
method is used to assign the final product’s states. Compared the vibrational
state population shown in Fig.S2 with those obtained on the 3A'' PES [Fig.7
in the paper], we can conclude that both sets of vibrational state distribution
exhibit the same general trends for all the collision energies considered in
this work. However, the HS rotational state distributions for the exchange
channel calculated on the 3A' PES exhibit different behavior, as shown in
right panels of Fig.S3. At Ecol=2.0 eV, the HS rotational state distributions for
all the final v’ states are similar to those calculated on the 3A'' PES. The ICS
increases with j’ and reaches a maximum at an intermediate j’. In contrast,
for Ecol=0.5 and 1.0 eV, the HS rotational state distributions are different in
shape for lower v’ states, with the HS products are predominantly generated
in the ground rotational state. The differences observed between the 3A'' and
3
A' PES at low Ecol may arise from the dissimilarities on the H-S-H
non-linear regions of the potentials. As noted in the paper, the 3A' PES has a
higher barrier height than the 3A'' surface when the H-S-H bond deviates
from the linear arrangements. For example, the barrier height for 3A' PES is
20.74 kcal/mol, whereas the 3A'' surface is 9.39 kcal/mol when the H-S-H
bond angle is equal to 150º.
Finally, the state-to-state DCSs for abstraction and exchange processes for
the 3A' PES at Ecol=1.0 and 2.0 eV are shown in Fig.S4 and S5, respectively.
The corresponding results on the 3A' PES are similar to those obtained on the
3
A'' PES. In addition, the microscopic reaction mechanisms, either
“rebound”/“stripping”
for
the
abstraction
reaction
or
“direct
abstraction”/“migratory” for the exchange reaction, are also found for the
title reaction when the 3A' PES is employed.
Figure Captions
Fig.S1 Comparison of the QCT-GB and QCT-HB product rotational state
distributions in the reaction H + H′S(v=0, j=0) for v’=1-3 at Ecol=1.0 eV,
calculated on the 3A'' PES. Top panel: for the abstraction channel; bottom
panel: for the exchange channel. Squares: QCT-HB; open circles:
QCT-GB results.
Fig.S2 Product vibrational state distributions for the H + H′S(v=0, j=0)
reaction calculated on the ground 3A' PES. (a) for the H′H+ S abstraction
channel; (b) for the HS +H′ exchange channel.
Fig.S3 Product rotational state distributions for the H + H′S(v=0, j=0)
reaction at three collision energies calculated on the 3A' PES. Left panels
(a-c): for the abstraction channel; Right panels (a’-c’): for the exchange
channel.
Fig.S4 The state-to-state DCSs calculated by QCT-GB method on the 3A'
PES for the H+H′S → HH′+S reaction. The horizontal dotted lines
represent the maximum j’ predicted for the direct mechanism by the
kinematic model of Ref.42. Left panels: At collision energy of 1.0 eV;
Right panels: at collision energy of 2.0 eV.
Fig.S5 Same as Fig.4, but for the exchange reaction.
Fig.S1
Fig.S2
Fig.S3
Fig.S4
Fig.S5