QUASICLASSICAL TRAJECTORY STUDY

OF STEREODYNAMICS FOR THE

REACTIONS LI HF/DF/TF
JIE CHENG and XIAN-FANG YUE
*
Department of Physics and Information Engineering
Jining University, Qufu 273155, P. R. China
*
xfyuejnu@gmail.com
Received 6 May 2012
Accepted 26 October 2012
Published 8 February 2013
Stereodynamics of the reaction Li HF v 0. j 0 ! LiF H and its isotopic variants on
the ground electronic state (1
2
A
0
) potential energy surface (PES) are studied by employing the
quasiclassical trajectory (QCT) method. At a collision energy of 2.2 kcal/mol, product
rotational angular momentum distributions, P0
r
and Pc
r
, are calculated in the center-of-
mass (CM) frame. The results demonstrate that the product rotational angular momentum j
0
is
not only aligned along the direction perpendicular to the reagent relative velocity vector k, but
also oriented along the negative y-axis. The four generalized polarization-dependent dierential
cross sections (PDDCSs) are also computed. The PDDCS
00
distribution shows a sideways
scattering for the reaction Li HF and a strongly backward scattering for the reaction Li DF.
However, it displays both the forward and backward scatterings for the reaction Li TF. These
features demonstrate that the Li HF and Li DF reactions proceed predominantly through
the direct reaction mechanism. However, the Li TF reaction undergoes both the direct and
indirect reaction mechanisms. The PDDCS
21
distribution indicates that the product angular
distributions are anisotropic.
Keywords: Quasiclassical trajectory; stereodynamics; isotope eect; reaction mechanism.
1. Introduction
The Li HF ! LiF H reaction, as one of the simplest reactive collision systems
involving three dierent atoms, has become a benchmark for experimental and
theoretical studies in the eld of chemical reaction dynamics. Similar to other alkali-
hydrogen halide reactions (M HX ! MX H, M alkali metal, X halogen),
both the reagents HX and products MX have strong dipole moments, which allow
*Corresponding author.
Journal of Theoretical and Computational Chemistry
Vol. 12, No. 3 (2013) 1350008 (11 pages)
#.
c World Scientic Publishing Company
DOI: 10.1142/S0219633613500089
1350008-1
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the preparation of the reagents in specic initial states, and the determination of the
nal states of the products by linearly polarized laser techniques. Becker et al.
1
carried out the rst crossed molecular beam (CMB) study on the reaction Li HF !
LiF H in 1980. They measured the angular distributions of the LiF products for the
title reaction at several collision energies. At E
c
3.0 and 8.7 kcal/mol, the time-of-
ight (TOF) spectra of product velocity distributions was also measured by the
authors. The center-of-mass (CM) angular distribution shows evidence of complex
formation with near forwardbackward symmetry at E
c
3.0 kcal/mol, while the
strongly forward peaked angular distributions were found at E
c
8.7 kcal/mol.
Dierent product angular distributions were interpreted as changing of the reaction
mechanisms from long lived complex formation at E
c
3.0 kcal/mol to a direct
process at E
c
8.7 kcal/mol. Loesch and coworkers performed a series of CMB
experiments on inuences of reagent alignment,
2
translational energy,
3
vibrational,
2,4
and rotational excitations
5
for the Li HF ! LiF H reaction. In
their studies, the alignment of the reagent HF internuclear axis was achieved by
changing the direction of the guiding eld. The product angular distributions, the
partition of available energy and the integral reaction cross sections (ICSs) showed a
marked dierence for three dierent alignments of the HF internuclear axis (namely
an isotropic distribution, two others with the molecular axis preferentially aligned
along and perpendicular to the relative velocity vector of reagents).
Theoretically, Aguado et al.,
6,7
Parker et al.,
8
Jasper et al.,
9
and Burcl et al.
10
have constructed the ground and excited electronic states potential energy surfaces
(PESs) of the LiFH system. Employing these PESs, a number of quasiclassical tra-
jectory (QCT),
4,11
time-independent quantum dynamics,
7,12
and time-dependent
wave packet (WP)
1315
calculations have been carried out to penetrate reaction
dynamics of the title reactions. Very recently, Zanchet et al.
14
investigated the
dierential cross sections (DCSs) and product rotational polarization for the Li HF
reactions using a new WP code, MAD-WAVE3. They presented a rst exact
quantum calculation result for state-to-state DCSs, as well as product rotational
alignment for the Li HF v 0. j 0 ! LiF v
0
. j
0
H reaction at collision
energies of 2.2, 3.1 and 5.6 kcal/mol, respectively. Gonzalez-Sanchez et al.
15
per-
formed the state-to-state Li HF v. j. m ! LiF v
0
. j
0
. m
0
H reactions using a
WP method. They found that the reactivity is enhanced for nearly collinear col-
lisions. The LiF (v
0
0) products are preferentially forward scattered, while vibra-
tionally excited LiF (v
0
1 and 2) are backward scattered. Their results are
interpreted as being due to the later barrier, bent geometry of the transition state,
and a covalent/ionic crossing. However, few studies pay attention to the isotope
eect on the dynamics of the title reaction.
In the present work, we carry out the stereodynamic calculations on the
Li HF v 0. j 0 ! LiF H R1, Li DF v 0. j 0 ! LiF D R2 and
Li TF v 0. j 0 ! LiF T R3 reactions at E
c
2.2 kcal/mol by employing
the QCT method. The isotope eect on product rotational angular momentum
polarization and product angular distribution is revealed and discussed.
J. Cheng & X.-F. Yue
1350008-2
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2. Calculating Scheme
An accurate and popular ground state (1
2
A
0
) PES
6
is used in the present calcu-
lations. This PES is constructed by Aguado et al.
6
and called AP2 PES in previous
literatures. The system presents a relatively deep well of 0.279 eV in the entrance
channel, corresponding to the Li-FH complex. In the exit channel, there is a later
barrier with an elongated HF bond length of 1.301

A. This barrier is the result of a

curve crossing between a covalent and ionic electronic states, corresponding with
Li
2
S HF
1
P

and Li

1
S HF
7
. The main feature of this PES are sum-
marized in Fig. 1. More details of the PES can be found in Ref. 6.
The general methodology of the QCT calculation is the same as used in previous
studies,
1621
which has been successfully applied to investigate a great deal of col-
lision reaction systems.
2231
At collision energy of 2.2 kcal/mol, batches of 500,000
trajectories have been calculated for each trajectory calculation. With the sixth order
symplectic integration method, an integration step of 1 10
16
s ensured a con-
servation of total energy and total angular momentum better than 1 in 10
5
and 10
7
,
Fig. 1. Minimum energy path and contour plots of the LiFH PES of Ref. 6 (top panels), and dierent
two-dimensional cuts of the PES to show the deep well in the entrance channel at \LiFH 107.4

(bottom left panel), as well as the saddle point at r

HF
1.301

A 2.46 Bohr (bottom right panel).

Quasiclassical Trajectory Study
1350008-3
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respectively. Since the potential has long range forces in both the entrance and exit
channels, the trajectories were started and nished at a distance from the lithium
atom to the center of mass of the diatom HF/DF/TF of 20.0

A. The value of the

maximum impact parameter, b
max
, is 1.948, 1.210 and 0.631

A for reactions R1, R2

and R3, respectively. The value of b is selected by b u
1,2
b
max
, where u is a random
number in the [0, 1] interval. The vibrational and rotational levels of the reagent
molecules are taken to be v 0 and j 0, respectively. The atom mass is chosen to
be 6.941 u for Li, 18.9984 u for F, 1.008 u for H, 2.014 u for D, and 3.016 u for T,
respectively.
The CM frame has been used as the reference frame in the present study, which is
depicted in Fig. 2. The reagent relative velocity vector k is parallel to the z-axis. The
xz plane is the scattering plane which contains the initial and nal relative velocity
vectors, k and k
0
. The 0
t
is the angle between the reagent relative velocity and the
product relative velocity (so-called scattering angle). The 0
r
and c
r
are the polar and
azimuthal angles of the nal rotational angular momentum j
0
. The general theory of
the product rotational polarization is standard.
17,18
The distribution function P0
r
describing the kj
0
correlation can be expanded
as a series of Legendre polynomials
P0
r

1
2
X
k0
ka
k
0
P
k
cos 0
r
. 1
where k 2k 1. The a
k
0
coecients are given by:
a
k
0
hP
k
cos 0
r
i
1
N
r
X
N
r
i1
P
k
cos 0
r
. 2
The expanding coecients a
k
0
are called orientation (k is odd) and alignment (k is
even) parameters. The angular brackets represent the Monte Carlo average over the
total number of reactive trajectories N
r
.
Fig. 2. The CM coordinate system used to describe k, k
0
and j
0
correlations.
J. Cheng & X.-F. Yue
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The dihedral angle distribution function Pc
r
describing kk
0
j
0
correlation
can be expanded as Fourier series
Pc
r

1
2
1
X
even.n!2
a
n
cos nc
r

X
odd.n!1
b
n
sin nc
r
!
. 3
where a
n
2hcos nc
r
i and b
n
2hsin nc
r
i.
The generalized polarization-dependent dierential cross sections (PDDCSs) are
written as:
2
o
do
kq
d.
t

X
k
1
1
2
k
1
S
k
1
kq
C
k
1
q
0
t
. 0. 4
where o is the integral cross section, o b
2
max
N
r
N
tot
. N
tot
is the total number of
trajectories. C
kq
are the modied spherical harmonics, C
kq

4
2k1

1,2
Y
kq
0. c. S
k
1
kq
is evaluated by using the expected value expression to be:
S
k
1
kq
hC
k
1
q
0
t
. 0C
kq
0
r
. 01
q
e
iqc
r
e
iqc
r
i. 5
The angular brackets represent the Monte Carlo average over the total number of
reactive trajectories N
r
. PDDCS
00

2
o
do
00
d.
t
, PDDCS
20

2
o
do
20
d.
t
, PDDCS
22

2
o
do
22
d.
t

and PDDCS
21

2
o
do
21
d.
t
are calculated in our study. We get a good convergence
results for the P0
r
. Pc
r
and PDDCSs when they are expanded up to k 18,
n 24 and k
1
7, respectively.
3. Results and Discussion
The calculated product P0
r
distributions of the reactions Li HF !
LiF H R1, Li DF ! LiF D R2 and Li TF ! LiF T R3 are plotted
in Fig. 3. Obviously, each P0
r
distribution of these three reactions is symmetric
with respect to 0
r
90

, and shows a distinct peak at 0

r
90

. This indicates that

the product rotational angular momentum vector j
0
is aligned perpendicular to the
relative velocity direction k. An outstanding trend is easily observed that the product
P0
r
distribution becomes lower and broader with the reactions varying from R1 to
R2, and then to R3. This means that the product rotational alignment becomes
weaker with increasing atomic mass of hydrogen isotopes. As discussed by Wang
et al.,
17,18
P0
r
is sensitive to two factors: one is the character of the PES and the
other is the mass factor (i.e. cos
2
u m
A
m
C
,m
A
m
B
m
B
m
C
for the reaction
A BC ! AB C. In the present calculations, the same adiabatic PES of the
ground 1
2
A
0
electronic state was adopted. Therefore, the dierence between P0
r

distributions is most attributed to the dierence in mass factor between the reactions
R1 (cos
2
u 0.013, R2 (cos
2
u 0.026 and R3 (cos
2
u 0.037.
Under the c
r
denition of the dihedral angle between the planes consisting of
kk
0
and kj
0
, the Pc
r
distribution can provide both product rotational align-
ment and orientation information. Figure 4 displays the Pc
r
distributions for the
Quasiclassical Trajectory Study
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reactions R1, R2 and R3, respectively. A common feature is easily found from Fig. 4
that the Pc
r
distributions are asymmetric with respect to the scattering kk
0
plane for these three reactions. The Pc
r
distributions of reactions R1 and R2 have
almost the same large peak at c
r
270

. However, they demonstrate a tiny peak at

c
r
90

for the reaction R1, but no peak at c

r
90

for the reaction R2. For the

Fig. 4. Pc
r
distributions as a function of the dihedral angle c
r
for the Li HF ! LiF H, Li DF !
LiF D and Li TF ! LiF T reactions (from inner to outer).
Fig. 3. P0
r
distributions as a function of the polar angle 0
r
for the Li HF ! LiF H, Li DF !
LiF D and Li TF ! LiF T reactions.
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reaction R3, the Pc
r
distributions show a small peak at c
r
270

, and no peak at
c
r
90

for the reaction R3. These features convey the information to us that most
products tend to align along the direction of y-axis which is perpendicular to the
scattering kk
0
plane, and the orientation of the product rotational angular
momentum tends to point to the direction of negative y-axis. That is to say, the
product molecules prefer a counterclockwise rotation (see from the direction of
negative y-axis) in the plane parallel to the scattering plane. This indicates that the
product rotational orientation becomes weaker with the increase of atomic mass of
hydrogen isotopes.
Such orientation preference could be explained qualitatively with an \impulsive
model" for atom and molecule collisions.
32
According to this impulsive model, for
the reaction A BC ! AB C, the product angular momentum vector j
0
is
expressed by j
0
Lsin
2
u j cos
2
u J
1
m
B
,m
AB
, where L is the reagent orbital
angular momentum and j is the reagent rotational angular momentum. J
1

j
BC
E
r
p
r
AB
r
CB
, with r
AB
and r
CB
being the unit vectors and B pointing to A
and C, respectively, j
BC
is the reduced mass of the BC molecule and E
r
is the
repulsive energy between B and C atoms. The cos
2
u is mass factor, and
sin
2
u 1 cos
2
u. Here, A represents Li atom, B represents F atom and C represents
H/D/T atoms, respectively. As described above, the rst and second terms are
symmetric with respect to the scattering plane. Therefore, the preferred direction of
the product angular momentum is determined only by the third term

j
BC
E
r
p
r
AB
r
CB
, which is traced back to the repulsive energy E
r
of BC molecule.
As a consequence, we can say that the repulsive energy E
r
mostly leads to the
product counterclockwise rotation.
The generalized PDDCSs describe the kk
0
j
0
correlation and the scattering
direction of the product molecule. Figure 5 shows the calculated results of the
PDDCSs for the reactions R1, R2 and R3. The DCS,
do
R
d.
, is simply proportional to
the PDDCS
00
,
do
R
d.

o
R
2
PDDCS
00

o
R
2

1
2

P
n
a
n
P
n
cos 0
t
. Whose coecient a
n
are given as a
n

2n1
2
hP
n
cos 0
t
i. The calculated DCS distribution for the Li
HF v 0. j 0 ! LiF H reaction is demonstrated in Fig. 6. For comparison,
previous results of DCS for the Li HF reaction calculated by the WP method by
Zanchet et al.
14
and the QCT method by Bobbenkamp et al.
5
are also displayed in
Fig. 6. Obviously, the DCS distribution of our present QCT results is very dierent
with the WP results of Zanchet et al.
14
and QCT results of Bobbenkamp et al.
5
This
dierence may ascribe to dierent PESs used by Zanchet et al.
14
and Bobbenkamp
et al.
5
and our present work. The Zanchet's and Bobbenkamp's calculations were
based on the APW
33
(A. Aguado, M. Paniagua and H. J. Werger) PES, but our
computations were based on the AP2 PES. Under the same APW PES, the DCSs of
the QCT
5
and WP
14
results also present signicant dierences, which are attributed
to quantum eects on the Li HF ! LiF H reaction.
14
Figure 5(a) presents the
PDDCS
00
as a function of scattering angle 0
t
for these three reactions. As clearly seen
in Fig. 5(a), the PDDCS
00
distribution shows a sideways scattering for the reaction
R1. For the reaction R2, the PDDCS
00
distribution exhibits a strong backward
Quasiclassical Trajectory Study
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scattering. Features of the PDDCS
00
distributions in the reactions R1 and R2 imply
that the reaction mechanism of the Li HF and Li DF is mainly direct reaction
process. Nevertheless, the PDDCS
00
distribution behaves as both the forward and
backward scatterings for the reaction R3, with a dominant forward scattering
between 0
t
0

and 30

. The character of the PDDCS

00
distributions in the reaction
R3 means that the reaction mechanism of the Li TF reaction is both the direct and
indirect reaction processes. The PDDCS
20
distribution demonstrates an opposite
trend to that of the PDDCS
00
, which may result from the fact that the PDDCS
20
is
related to alignment moment hP
2
cos 0
r
i. When the product rotational angular
momentum j
0
is perpendicular to k, the hP
2
cos 0
r
i equal to 0.5. For the reactions
R1 and R2, all of the PDDCS
20
values are negative for all scattering angles, which
suggests that the product rotational angular momentum j
0
polarizes preferentially
along the direction perpendicular to k. This is consistent with the product alignment
(a) (b)
(c) (d)
Fig. 5. Panels (a) and (b) show the PDDCSs with k. q 0. 0 and (2, 0), respectively. Panels (c) and
(d) show the PDDCSs with k. q 2. 2 and (2, 1), respectively.
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1350008-8
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prediction of the P0
r
distribution depicted in Fig. 2. For the reaction R3, the
PDDCS
20
has very small positive values at scattering angles ranging from 0
t
39

to
62

, but positive values at other scattering angles. This phenomenon may interpret
that the alignment of the LiF product from the reactions R1 and R2 are stronger
than that of the reaction R3.
Figures 5(c) and 5(d) depict the PDDCS distributions with q 6 0. All of the
PDDCS with q 6 0 are equal to zero at the extremities of forward and backward
scatterings. At these limits of scattering angle, the kk
0
scattering plane is not
determined and the values of the PDDCS with q 6 0 must be zero. The behavior of
PDDCS with q 6 0 at scattering angles away from extreme forward and backward
direction is more interesting, which can provide detailed information about the
product rotational alignment and orientation. The PDDCS
22
is related to
hsin
2
0
r
cos 2c
r
i. The negative values of the PDDCS
22
correspond with the product
rotational alignment along the y-axis, while the positive values with the rotational
alignment along the x-axis. The larger the absolute value is, the stronger the product
rotational alignment is along the corresponding axis. As shown in Fig. 5(c), the
PDDCS
22
distribution for these three reactions show the negative values for all
the scattering angles. This demonstrates that the product j
0
alignment is along the
y-axis, which is consistent with the Pc
r
distributions described in Fig. 3. The
PDDCS
21
is related to hsin 20
r
cos c
r
i, and its behavior is similar with that of
the PDDCS
22
. The PDDCS
21
is positive or negative, corresponding to the product
rotational angular momentum j
0
along the directions of vector x z or x z. As
shown in Fig. 5(d), the PDDCS
21
values vary with the dierent scattering angles,
which imply that the product angular momentum distributions are anisotropic. For
the reaction R3, the PDDCS
21
distribution shows a strongest negative peak at
Fig. 6. DCSs of our present results for the Li HF ! LiF H reaction compared with previous WP
results by Zanchet et al.
14
and QCT results by Bobbenkamp et al.
5
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0
t
34

and a strongest positive peak at 0

t
87

. They exhibit two moderate

negative peaks at scattering angles at 0
t
34

and 148

, as well as a moderate
positive peak at 0
t
87

for the reaction R2. However, there are no large positive

and negative peaks for the reaction R3. These features demonstrate that the
rotational alignment of the LiF products is not only along the x z, but also along
the x z directions for the title reactions. The product rotational alignments of LiF
for the reaction R3 are weaker than that for the reactions R1 and R2. This is
consistent with the product polarization information displayed in Figs. 3 and 4.
4. Conclusion
QCT calculations have been performed on stereodynamics study for the reactions
Li HF v 0. j 0 ! LiF H R1, Li DF v 0. j 0 ! LiF D R2 and
Li TF v 0. j 0 ! LiF T R3 at the collision energy of 2.2 kcal/mol. Two
product rotational angular momentum distributions, P0
r
and Pc
r
, and four
generalized PDDCSs were computed and analyzed. The P0
r
exhibits a symmetric
distribution with respect to 0
r
90

, with a prominent peak at 0

r
90

for each of
the reactions R1, R2 and R3. With increasing the atomic mass of the hydrogen
isotopes, the peak at 0
r
90

becomes weaker. The Pc

r
distribution shows a large
peak at c
r
270

for the reactions R1 and R2, however, it displays a mall peak at

c
r
90

for the reaction R1, and no peak at c

r
90

for the reaction R2. For the

reaction R3, the Pc
r
distribution shows a moderate peak at c
r
270

and no peak
at c
r
90

. These results indicate that the product rotational angular momentum j

0
is not only aligned along the direction perpendicular to the reagent relative velocity
k, but also oriented along the direction of the negative y-axis. The PDDCS
00
dis-
tributions illustrate sideways scattering for the reaction R1 and strongly backward
scattering for the reaction R2, whereas, they manifest both the forward and back-
ward scatterings for the reaction R3, with a strong bias in the forward scattering.
This means that the reactions R1 and R2 are mainly direct reaction mechanism,
however, the reaction R3 are both the direct and indirect reaction mechanisms. The
PDDCS
20
and PDDCS
22
distributions are consistent with angular momentum
distributions of the P0
r
and Pc
r
. The PDDCS
21
distribution demonstrates that
the product angular distributions are anisotropic.
Acknowledgments
The authors gratefully acknowledge the nancial support provided by the National
Natural Science Foundation of China (No. 21003062) and the Foundation for Out-
standing Yong Scientist in Shandong Province (No. BS2012SF002).
References
1. Becker CH, Casavecchia P, Tiedemann PW, Valentini JJ, Lee YT, J Chem Phys 73:
2833, 1980.
J. Cheng & X.-F. Yue
1350008-10
J
.

T
h
e
o
r
.

C
o
m
p
u
t
.

C
h
e
m
.

D
o
w
n
l
o
a
d
e
d

f
r
o
m

w
w
w
.
w
o
r
l
d
s
c
i
e
n
t
i
f
i
c
.
c
o
m
b
y

8
1
.
6
2
.
1
0
0
.
1
6
5

o
n

0
2
/
1
9
/
1
3
.

F
o
r

p
e
r
s
o
n
a
l

u
s
e

o
n
l
y
.
2. Loesch HJ, Stienkemeier F, J Chem Phys 98:9570, 1993.
3. Hobel O, Bobbenkamp R, Paladini A, Russo A, Loesch HJ, Phys Chem Chem Phys
6:2198, 2004.
4. Aoiz FJ, Verdasco E, Rabanos VS, Loesch HJ, Menendez M, Stienkemeier F, Phys Chem
Chem Phys 2:541, 2000.
5. Bobbenkamp R, Paladini A, Russo A, Loesch JJ, Menendez M, Verdasco E, Aoiz FJ,
Werner HJ, J Chem Phys 122:244304, 2005.
6. Aguado A, Paniagua M, Lara M, Roncero O, J Chem Phys 107:10085, 1997.
7. Aguado A, Paniagua M, Sanz C, Roncero O, J Chem Phys 119:10088, 2003.
8. Parker GA, Lagan A, Crocchianti S, Pack RT, J Chem Phys 102:1238, 1995.
9. Jasper AW, Hack MD, Truhlar DG, Piecuch P, J Chem Phys 116:8353, 2002.
10. Burcl R, Piecuch P, pirko V, Bludsk O, Int J Quantum Chem 80:916, 2000.
11. Yuan MH, Zhao GJ, Int J Quantum Chem 110:1842, 2010.
12. Wei L, Jasper AW, Truhlar DG, J Phys Chem A 107:7236, 2003.
13. Zhu W, Wang D, Zhang JZH, Theor Chem Acc 96:31, 1997.
14. Zanchet A, Roncero O, Gonzalez-Lezana T, Rodrguez-Lopez A, Aguado A, Sanz-Sanz C,
Gomez-Carrasco S, J Phys Chem A 113:14488, 2009.
15. Gonzalez-Sanchez L, Vasyutinskii O, Zanchet A, Sanz-Sanz C, Roncero O, Phys Chem
Chem Phys 13:13656, 2011.
16. Han KL, He GZ, Lou NQ, J Chem Phys 105:8699, 1996.
17. Wang ML, Han KL, He GZ, J Phys Chem A 102:20204, 1998.
18. Wang ML, Han KL, He GZ, J Chem Phys 109:5446, 1998.
19. Han KL, Zhang L, Xu DL, He GZ, Lou NQ, J Phys Chem A 105:2956, 2001.
20. Chen MD, Han KL, Lou NQ, J Chem Phys 118:4463, 2003.
21. Zhang X, Han KL, Int J Quantum Chem 106:1815, 2006.
22. Zhang WQ, Chen MD, J Theo Comput Chem 8:1131, 2009.
23. Zhang WQ, Zhang CH, Chen MD, J Theo Comput Chem 8:403, 2009.
24. Zhang CH, Zhang WQ, Cheng MD, J Theo Comput Chem 8:403, 2009.
25. Yue XF, Cheng J, Zhang H, J Theo Comput Chem 9:919, 2010.
26. Li YM, Wang S, J Theo Comput Chem 9:487, 2010.
27. Liu YF, He XH, Gao YL, Sun JF, J Theo Comput Chem 9:327, 2010.
28. Wei Q, Xie YK, Feng WL, J Theo Comput Chem 10:1, 2011.
29. Wei Q, Wu VWK, Zhou B, J Theo Comput Chem 8:1177, 2009.
30. Chen YY, Zhao MY, J Theo Comput Chem 11:87, 2012.
31. Yue XF, Geng JP, J Theo Comput Chem 11:35, 2012.
32. Li RJ, Han KL, Li FE, Lu RC, He GZ, Lou NQ, Chem Phys Lett 220:281, 1994.
33. Aguado A, Paniagua M, Werner HJ, unpublished, available at: http://www.theochem.
uni-stuttgart.de/werner/lihf/lihf.html, 2004.
Quasiclassical Trajectory Study
1350008-11
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o
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e
d

f
r
o
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w
w
w
.
w
o
r
l
d
s
c
i
e
n
t
i
f
i
c
.
c
o
m
b
y

8
1
.
6
2
.
1
0
0
.
1
6
5

o
n

0
2
/
1
9
/
1
3
.

F
o
r

p
e
r
s
o
n
a
l

u
s
e

o
n
l
y
.