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An accurate potential energy surface for the F + H2 → HF + H reaction by the

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 An accurate potential energy surface for the F + H2 → HF + H reaction by the
coupled-cluster method
Jun Chen, Zhigang Sun, and Dong H. Zhang

Citation: The Journal of Chemical Physics 142, 024303 (2015); doi: 10.1063/1.4904546
View online: http://dx.doi.org/10.1063/1.4904546
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/142/2?ver=pdfcov
Published by the AIP Publishing

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 THE JOURNAL OF CHEMICAL PHYSICS 142, 024303 (2015)

An accurate potential energy surface for the F + H2 → HF + H reaction

by the coupled-cluster method
Jun Chen, Zhigang Sun,a) and Dong H. Zhanga)
State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry,
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023,
People’s Republic of China
(Received 18 September 2014; accepted 26 November 2014; published online 8 January 2015)

A three dimensional potential energy surface for the F + H2 → HF + H reaction has been computed
by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadru-
ples [UCCSDT(2)Q] using the augmented correlation-consistent polarised valence quadruple zeta
basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis
set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock
orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS)
correction term was included. The global potential energy surface was calculated by fitting the
sampled ab initio points without any scaling factor for the correlation energy part using a neutral
network function method. Extensive dynamics calculations have been carried out on the potential
energy surface. The reaction rate constants, integral cross sections, product rotational states distribu-
tion, and forward and backward scattering as a function of collision energy of the F + HD → HF + D,
F + HD → DF + H, and F + H2 reaction, were calculated by the time-independent quantum dynamics
scattering theory using the new surface. The satisfactory agreement with the reported experimental
observations previously demonstrates the accuracy of the new potential energy surface. C 2015 AIP
Publishing LLC. [http://dx.doi.org/10.1063/1.4904546]

I. INTRODUCTION in the history. The first ab initio PES was constructed by

The success in theory and experiment for the H + H2
→ H2 + H reaction is a milestone in the development of chem-
ical kinetics and molecular dynamics, due to its theoretical and
experimental availability.1–4 Since the F + H2 → HF
+ H reaction and its isotopes have a great deal more “char-
acter” than the reaction of H + H2 → H2 + H, it provides the
next test of our capabilities in theory and experiment.5–15
As such, the F + H2 → HF + H reaction is highly exoergic
(by 32.001 kcal/mol) and produces vibrationally excited HF,
which is the energy source for powerful chemical lasers,
and supports fascinating quantum mechanical resonances.
The dynamics of the reaction can be studied by a variety of
experimental techniques, and has received extensive experi-
mental studies by using high resolution molecular crossing
beams,5,7–9,13,16,17 chemiluminescence experiments,18–20 and
chemical lasers.11,12,21,22
The reaction F+H2 → HF+H presents greater theoretical
difficulties and thus a greater challenge than the H + H2 → H2
+H reaction. With strongly coupled eleven electrons, compared
to three, the FHH system requires much more elaborate calcu-
lations in the determination of potential energies with high
accuracy. In addition, the F + H2 reaction has multiple poten-
tial energy surfaces (PESs) accessible at ordinary tempera-
tures. Due to its importance, a lot of PESs have appeared
a)Authorsto whom correspondence should be addressed. Email:
zsun@dicp.ac.cn and zhangdh@dicp.ac.cn.
Bender, O’Neil, Pearson, and Schaefer (BOPS) in 1972 using
a comparatively small orbital basis set and first order configu-
ration interaction (FOCI) wave functions.23,24
However, limited by the computational resources of the
time, an accurate global ab initio surface was impossible. The
first empirical surface of the London–Eyring–Polanyi–Sato
(LEPS) type was constructed by Muckerman (hereafter, M5),
which had been the most successful until 1985.25 The M5
surface has a collinear barrier height of 1.06 kcal mol−1. Its
bending potential is tighter than that of the BOPS PES. Ap-
proximate quantum mechanics (QM) methods and quasi clas-
sical trajectory (QCT) calculations carried out on this PES
were able to reproduce the measured v ′ branching ratios and
the activation energy deduced from the kinetic data available
at that time. However, it is unable to reproduce the observed
v ′-specified forward scattering peak. Another empirical PES
of the LEPS type, which has a bent transition state, was con-
structed by Takayanagi and Sato (TS) in 1988.26 The TS PES
has a collinear barrier height of ∼ 0.78 kcal mol−1 and a negli-
gible bent barrier. The trajectory calculations on this surface
showed for the first time that the product v ′-specified forward
peaks in the DCS could also be obtained in classical mechanics
calculations.
A series of semiempirical PES (called T5, T5A, SEC5, and
SEC6) with successive refinements in the ab initio treatment of
the transition state were constructed by the group of Truhlar
around 1990,27–31 in an attempt to resolve the difficulty in
producing the observed forward peaks. These surfaces have
bent barrier heights of 0.7 ∼ 1.1 kcal mol−1 and gave good

0021-9606/2015/142(2)/024303/11/$30.00 142, 024303-1 © 2015 AIP Publishing LLC

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 024303-2 Chen, Sun, and Zhang
thresholds of the vibrational product. They overall are able to
approximately reproduce the observed forward scattering in
the molecular crossing beam experiments, but fail to account
for the product vibrational state distributions.32,33
In 1996, a PES based on very high level ab initio calcu-
lations was published by Stark and Werner (SW).15 In the
calculation, total 714 ab initio points were obtained using
the internally contracted multireference configuration inter-
action (MRCI) method with the Davidson correction (MRCI
+Q) and complete active space self-consistent field (CASSCF)
reference functions. The global analytical fit of the potential
(without the effect of spin-orbit coupling) was given using the
analytic polynomials. The SW PES is able to reproduce quan-
titatively the FH−2 photoelectron spectrum34–36 and the step in
the excitation function at collision energy of 0.5 kcal mol−1
of the F + HD → HF + D reaction observed by Liu and his
coworkers.5,17 Especially, the forward scattering peaks in the
DCS could be reproduced by both the QM and QCT theory
using the SW PES, even the QCT theory gives much lower
ones.37,38 The SW PES can predict well the branching ratios
and reaction rate constants of the F+HD reaction also.39 How-
ever, soon it was found that the SW PES is unable to reproduce
the experimental observations satisfactorily in a wide range.
Such as, the energy of the asymptotic channels was missed by
about 11 meV. This mismatch in the reaction exothermicity
is also further enhanced when the spin-orbit interaction of
the fluorine atom is considered. The SW PES cannot account
for the sharp increase of the HF(′v = 3) yield in the F + HD
reaction as a function of collision energy as soon as this channel
becomes energetically allowed either.39
In view of these drawbacks, considerable theoretical effort
has been spent on improving the accuracy of the SW PES,
which in turn was proved to be unsatisfactory.40–43 In 2006,
Xu, Xie, and Zhang (XXZ) used large-scale multireference
configuration-interaction calculations, with a slightly better
basis set than that used by Stark and Werner,15 for determin-
ing many energy points of the F + H2 reaction.44 The barrier
properties of the XXZ surface are very similar to those of
the HSW (Hartke-Stark-Werner) surface,36 which was con-
structed by including the spin-orbit effects to the original SW
PES. However, the XXZ PES is quite different from the SW
or HSW PES around the van der Waals well in the product
channel. The XXZ PES is able to reproduce accurately the
peak of the forward scattering as a function of collision en-
ergy at 0.5 kcal mol−1 of the F + H2 reaction.7 However, soon
later investigation disclosed that the XXZ PES is unable to
satisfactorily describe the reactive resonances in the isotope
substituted reaction F + HD → HF + D. 9
In 2008, Fu, Xu, and Zhang (FXZ) constructed another
PES based on the UCCSD(T) (spin unrestricted coupled cluster
method with all single and double excitations and perturbative
accounts of triple excitations) level of calculations.9,45 The
correlation energies for the high level ab initio data points of
the FXZ PES were scaled by a factor of 1.01 in order to get
the correct exothermicity of 32.00 kcal/mol with the spin-orbit
interaction energy considered. The global PES was obtained
by using the B-spline interpolation method on the dense ab
initio points, same as that in the XXZ PES. Quantum dynamics
studies show that the FXZ PES is able to describe very well
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J. Chem. Phys. 142, 024303 (2015)
the resonance states in both the F + H2 and F + HD reaction9
and the slow-down mechanism in the F + H2 → HF(v′ = 3) + H
reaction.8 Extensive quantum dynamics studies on the FXZ
PES by Fazio et al. also suggested that the FXZ PES can
be considered as a significant advancement compared to pre-
vious PESs, especially on reproducing the sharp increase of
the HF(v ′ = 3) yield in the F + HD reaction as a function of
collision energy as soon as this channel becomes energetically
allowed.39
The reaction F + H2 is also a prototype for studying the
spin-orbit effects.46,47 The full description of the reaction F+H2
→ HF+H involves four electronically diabatic PES, as well as
two geometry-dependent spin-orbit terms.48 Diagonalization
of the diabatic Hamiltonian gives rise to three fully adiabatic
potential energy surfaces, of which only the lowest correlates
with HF + H products in their electronic ground state. Based
on the data calculated using six-state basis, in 2000, Alexander,
Stark, and Werner (ASW) constructed a set of diabatic sur-
faces.48 The lowest adiabatic sheet of the ASW PES is virtually
identical to the SW surface in the region of the barrier and the
product arrangement, but lies ∼0.39 kcal mol−1 lower in the
reactant asymptote. In 2007, Li, Werner, and Alexander (LWA)
carried out MRCI+Q/aug-cc-pV5Z level of ab initio calcu-
lations and fitted two versions of nonadiabatic PESs for the
FH2 system according to the scaling factors for the correlation
energy: LWA-5 and LWA-78, for a scaling factor of 1.05 and
1.078, respectively.49 Nonadiabatic quantum dynamics carried
out on the LWA-78 PES produced differential cross sections
and reactivity ratio between F (2P3/2)+D2 and F (2P1/2)+D2 in
excellent agreement with the latest experiment.49 However, on
accounting for the reactive resonance states in the F + H2 and
F + HD reaction, the adiabatic FXZ PES is more accurate.45
In 2008, Werner, Kállay, and Gauss carried out extensive
coupled-cluster and MRCI benchmark calculations for deter-
mining the barrier height of the F + H2 reaction as accurately
as possible.50 Without spin-orbit coupling, they gave the best
coupled cluster method with singles, doubles, triples, and per-
turbative quadruples (CCSDTQ) estimation for barrier height
of the bent transition state amounts to 1.26 kcal/mol, which
is almost 0.3 kcal/mol lower than the barrier height of the
SW surface. If the spin-orbit corrections are included, they
predicted that the linear and bent barrier heights were 2.16
and 1.63 kcal/mol, respectively, with uncertainty of about 0.05
∼ 0.1 kcal mol−1. This bent barrier height is a little lower than
that of the FXZ PES (1.76 kcal mol−1).
In order to investigate the barrier height effect of the FXZ
PES on describing the reactions, and to refine the FXZ PES, in
this study, a new PES (Chen-Sun-Zhang PES, hereafter, CSZ
PES) was constructed at the spin unrestricted coupled cluster
method with singles, doubles, triples, and perturbative quadru-
ples [UCCSDT(2)Q] level. The CSZ PES does not require any
scaling factor for the correlation energies on the high level ab
initio data points and is fitted by the neutral network method.
This PES has been applied to investigate the reactive resonance
occurring in the reaction of the F+HD (v0 = 1, j0 = 0) reaction,
which suggested the accuracy of the new PES.51
In this work, we will demonstrate that the CSZ PES can
reproduce the experimental observations in many aspects, such
as the reaction rate constant and branch ratios of the reaction
 024303-3 Chen, Sun, and Zhang
F + HD/H2,5,17,52,61 forward/backward scattering as a function
of collision energy of the reaction F + HD/H2 and peaks indi-
cating partial waves resonance of the reaction F + HD,7,9,53 in
a slightly better way than the previous FXZ PES.
The remaining content of the paper is arranged as follows:
in Sec. II we describe the relevant details for constructing the
PES and for the time-independent quantum dynamics calcu-
lations. The comparison of the calculated reactive observables
with the experimental data is presented in Sec. III. Conclusions
are finally given in Sec. IV.
II. AB INITIO CALCULATIONS AND PES FITTING
For constructing the PES for the F + H2 reaction,
the ab initio calculations were carried out based on the
[UCCSD(T)] using the augmented correlation-consistent
polarized valence sextuple zeta basis set [aug-cc-pV6Z], as
well as the [UCCSDT(2)Q] using the augmented correlation-
consistent polarized valence quadruple zeta basis set [aug-cc-
pVQZ] for fluorine atom and correlation-consistent polarized
valence quadruple zeta basis set [cc-pVQZ] for hydrogen
atoms. All the calculations are based on restricted open-shell
Hartree-Fock [ROHF] orbitals, together with the frozen core
approximations.
Using the hierarchical construction scheme proposed in
the work by Fu, Xu, and Zhang,45 the final energy of the surface
was decomposed as the following 5 parts:
( UCCSD(T) )
Vtotal = V1
AVQZ
( UCCSD(T) ) ( UCCSD(T) )
+V2 − using the basis set AVQZ for F atom and VQZ for H atoms.
AV5Z AVQZ
( ( UCCSD(T) ) 5−3 
( UCCSD(T) ) )
+V3 − × −3 −3
AV6Z AV5Z 5 −6
( UCCSDT(2) ) ( UCCSD(T) ) 
Q
+V4 − respecting to F+H2 asymptotic. Using a NN structure of 3-20-
AVQZF/VQZH AVQZF/VQZH
( )
+V5 Spin Orbit ,
in which the AVQZ term V1 and the spin-orbit coupling term
V5 are taken from the FXZ PES9,45 and the remaining three
terms were fitted to a large number of ab initio energies using
neural network (NN) functions. NN is a general fitting method
which has been widely used in high dimensional PES fittings
in these two decades.54–57 The spin-orbit coupling term V5 is
thus included in the FXZ and CSZ PES in a way similar to
that of the HSW PES36 which has the zero point energy of
the reactants in the F(2P3/2) + H2 state, in contrast with the
ignorance of the spin-orbit coupling terms of the SW PES15
which has the zero point energy of the reactants in the unsplit
2
P state.
The CSZ PES was constructed in terms of the internal
coordinates r HH, r HF, and θ, where r HH is the distance between
the two H atoms, r HF is the distance between F and one of
the H atoms, and θ is the enclosed bond angle. For fitting
the surface using the NN method, we applied a feed forward
neural network function with two hidden layers, which has the
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J. Chem. Phys. 142, 024303 (2015)
following functional form:
K J
 
y = b31 + w1,k
3
· f 2 b2k + wk,
2 1 1
j · f bj
k=1 j=1
I

+ wj,i
1
· xi






,
i=1
where I is the degree of freedom of the system corresponding to
the number of bond lengths for a molecular configuration, J,K
defines the number of neurons used for fitting, x i (i = 1,...,I)
are the bond lengths for a molecular configuration, the weights
wj,i
l
connect the ith neuron of (l − 1)th layer and the j th neuron
of l layer, and the biases blj determine the threshold of the
th
j th neuron of l th layer, f 1 and f 2 are transfer functions taken
as hyperbolic tangent functions. The AV5Z correction term
V2 was fitted to 1882 [UCCSD(T)/AV5Z -UCCSD(T)/AVQZ]
ab initio energies, using a NN structure of 3-20-20-1, and to a
fitting error of 0.0022 kcal/mol. The CCSD(T)/CBS correction
term V3 was included by a fitting to 1184 [UCCSD(T)/AV6Z-
UCCSD(T)/AV5Z] energies using a NN structure of 3-15-15-
1, followed by extrapolating to the basis set limit using the
formula:
E Xcorr = E∞
corr
+ AX −3.
Because the Hartree-Fock energy almost converged at the
AV5Z and AV6Z level, the extrapolation of the total energy in
this PES was identical to that of the correlation energy. The
fitting error of this part is 0.0004 kcal/mol.
Finally, in order to account for the higher order excitation
level of the coupled cluster energy, we fitted the UCCSDT(2)Q-
UCCSD(T) correction term V4 based on 775 energy points,
Most of these points were located around the transition
state region, with r HF ≤ 4.5 bohrs and r HH ≤ 3.5 bohrs, and
with UCCSD(T)/AV5Z energies less than 18.4484 kcal/mol
20-1, one can get a fitting error of 0.0024 kcal/mol for V4 term.
The post-CCSD(T) effect is very small in the F + H2 entrance
channel, and no correction is applied when r HF > 4.5 bohrs.
For the HF + H asymptotic part, the correction term was
switched to a line of UCCSDT(2)Q and UCCSD(T) for HF
molecule when r HH > 3.5 bohrs. This part of UCCSD(T) and
UCCSDT(2)Q calculations at AVQZF/VQZH basis set were
accomplished with the NWchem58 package, but all of the
UCCSD(T) calculations at AVnZ(n = Q,5,6) were carried out
using the MOLPRO package.59 The present PES is expected
to be more accurate than the existing FXZ PES which was
based on the UCCSD(T)/AV5Z level. A scaling factor for the
correlation energy is not required for the present PES, as did
for the FXZ PES.
Figure 1 plots the potential energy curves around the
bent barrier of the SW, XXZ, FXZ, and CSZ PES, as a
function of θ, with fixed r HH and r HF. It is observed that
the SW PES has lowest bent barrier (1.53 kcal/mol, note:
without spin-orbit effects) but the XXZ PES has the highest
bent barrier (2.04 kcal/mol). The bent barrier of the CSZ
PES (1.68 kcal/mol) agrees well with the best estimation
(1.63 kcal/mol) using the CCSDTQ method by Werner, Kállay,
 024303-4 Chen, Sun, and Zhang J. Chem. Phys. 142, 024303 (2015)

FIG. 1. The barrier heights as a function of the enclosed bond angle θ for the
SW, XXZ, FXZ, and CSZ PES with fixed r HH and r HF.

and Gauss.50 The bent barrier properties of these four PES are
listed in Table I for a comparison.
In Fig. 2, we present the potentials in the entrance channel
for T geometries (Θ = 90◦ in Jacobi coordinates) as a function
of RHH–F and r HH = 1.40 bohrs, and the potentials in the exit
channel for collinear geometries as a function of r H–H and
r HF = 1.74 bohrs. It is observed that in the product channel, the
later three surfaces, XXZ, FXZ, and CSZ PES, are essentially
the same. However, in the entrance channel, both SW and XXZ
PES are quite different from the CSZ or FXZ PES, which are
quite similar. This may be due to the fact that none of them are
accurate enough around the van der Waals well in the entrance
channel.
The accuracy of the exothermicity of the surface for the
reaction F+H2 is very important, especially in comparison with FIG. 2. Top panel: The potentials in the entrance channel for T-shape ge-
ometries as a function of R HH–F and r HH = 1.40 bohr. Bottom panel: The
observation from a high-resolution molecular crossing beam
potentials in the exit channel for collinear geometries as a function of r H-H
experiment. The vibrational state-specified exothermicities of and r HF = 1.74 bohr. The zero energy is taken as the asymptotic static energy
these four PES are collected in Table II. Both the XXZ and in the entrance channel.
FXZ PES give excellent exothermicities, due to a correct
scaling factor for the correlation energy. The exothermicities
III. QUANTUM REACTIVE SCATTERING
of the CSZ PES are accurate also, even if it agrees with the
CALCULATIONS AND DISCUSSION
experimental values a little worse than those of the XXZ and
FXZ PES. We note that the LWA-78 and LWA-5 PES give The reaction F + H2 → HF + H is the main prototypical
exothermicity being as 32.05 and 31.90 kcal/mol, respectively. triatomic reaction for dynamical resonance and nonadiabatic
We stress the fact that the CSZ PES does not include any dynamics and has attracted enormous experimental and
scaling factor for the correlation energy of the original ab theoretical studies over the past decades. In the past years,
initio points. Yang and co-workers have carried out a series of experiments,

TABLE I. Comparison of bent barrier properties of different surfaces for the F + H2 reaction.

Surface R HF (bohrs) R HH (bohrs) Angle (◦) E (kcal/mol) ω s (cm−1) ω b (cm−1) ω a (cm−1)

SW (Ref. 15) 2.922 1.457 119 1.53 3758 277 715i

XXZ (Ref. 44) 2.91 1.457 119 2.04 3757 288 772i
FXZ (Ref. 45) 2.90 1.46 120 1.76 3808 313 740i
CSZ (current) 2.90 1.46 120 1.68 3808 313 732i

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 024303-5 Chen, Sun, and Zhang J. Chem. Phys. 142, 024303 (2015)

TABLE II. Vibrational state-specified exothermicities for the F + H2 reaction. Experimental values are taken from
Refs. 67–69.

∆E for F + H2 (v = 0, j = 0) → HF (v ′, j ′ = 0) + H

Surface v ′ = 0 (kcal/mol) v ′ = 1 (kcal/mol) v ′ = 2 (kcal/mol) v ′ = 3 (kcal/mol)

SW (Ref. 15) 31.66 20.36 9.54 −0.81

XXZ (Ref. 44) 31.99 20.67 9.83 −0.52
FXZ (Ref. 45) 32.02 20.68 9.85 −0.52
CSZ (current) 32.06 20.72 9.89 −0.47
Experimental 32.001 20.674 9.840 −0.516

using the high resolution and highly sensitive H-atom Rydberg
tagging method, to study the reaction system in great
detail.7–9,51,53
Correspondingly, the XXZ and FXZ PES were con-
structed, with increasing accuracy, in order to understand the
observed dynamic details.9,44,45 It has been shown that the XXZ
and FXZ PES can reproduce the experimental observation
from Yang’s group excellently at the time.7,9
In the work by Fazio et al.,39 extensive time-independent
quantum reactive scattering calculations were carried out for
the F+HD reaction using the FXZ PES. Vibrational branching
ratios, cross sections, and reaction rate constants are calculated
and compared with molecular beam scattering experiments as
well as with chemical kinetics data. They concluded that the
FXZ PES is a significant advancement compared with previous
PES. At the same time, they pointed out that the transition state
region of the FXZ PES still needs to be refined, in order to
better reproduce the experimental observation.
Therefore, it would be very interesting to see if the CSZ
PES, which has lower bent barrier and theoretically would be
more accurate, can reproduce the experimental observation in
molecular beams and the chemical kinetics data in a better
way.
Using rigorous time-independent quantum scattering
calculations on the new CSZ PES, we have studied the quantum
reaction dynamics of the F + H2 and F + HD reaction. Due to
the extremely low translational energy of a considerable part
of the product in the F + H2 and F + HD reaction, absorbing
potentials with very long range have to be applied in a time-
dependent quantum wave packet calculation. Therefore, in
this study, the calculations are carried out using an improved
parallelized version of the ABC code,60 which is parallelized
by an OpenMP multithreading implementation and without
data to be saved on the hard disk.
In Table III, we present the values of the input parameters
used in the calculations. In order to calculate the thermal
reaction rates of the F + HD → HF + D and DF + H reaction,
all of the state-to-state information for the initial states as
(v0, j0) = (0,0), (0,1), (0,2), and (0,3) have been calculated.
However, for the reaction rate constant of the F + H2 reaction,
only the state-to-state information for the initial states as
(v0, j0) = (0,0), (0,1), and (0,2) have been calculated.
In Fig. 3, the total reaction probabilities with J = 0
summed over all the open ro-vibrational states of the products
for both reaction channels of the F + HD reaction on the SW,
XXZ, FXZ, and CSZ PES are presented. A fine grid of 0.1 meV
in the whole energy range (0 ∼ 0.1 eV) is applied to resolve
most of the narrow long lived resonance features. The peaks
arising in the plots result from reactive resonances occurring
in the reactant or product channels. It is apparent from Fig.
3(b) that the XXZ, FXZ, CSZ, and SW PES have bent barrier
heights in an increasing order, since their reaction probabilities
arise in a decreasing order.
Similar to Fig. 3, total integral cross sections (ICS) calcu-
lated using the FXZ and CSZ PES for both reaction channels
are presented in Fig. 4, compared with the experimental
measurements by Liu and his coworkers.5,17 The numerical
predictions on the CSZ PES now agree better than the FXZ
PES, even it is still unable to qualitatively reproduce the DF
channel.
In Fig. 5, the theoretical reaction rate constants k(T)
calculated using the FXZ and CSZ PES for the production
of HF (upper panel) and DF (lower panel) at thermal and
subthermal regimes (150 ∼ 350 K) are compared with the
experimental data reported by Persky and Kornweitz.52,61 In
order to provide a complete picture, we also reproduce the
results calculated using the SW PES in Fig. 5 from Ref. 39
since the SW PES gives “good” reaction rate constant for the
DF channel. We observed from Fig. 5 that, comparing with
the FXZ PES, the CSZ PES can give better reaction rate con-
stant at higher temperature for the HF channel. However, now
the CSZ PES gives too large reaction rate constant at lower
temperature for the HF channel. For the DF channel, within
the plotted temperature range, the CSZ PES gives reaction
rate constant agrees better with the experimental observation
but in a similar slope, comparing with that of the FXZ PES.
The theoretical reaction rate constant for the DF channel is
still too low.
In the work by Fazio et al.,39 they ascribe the reason
for the failure of the FXZ PES for accurately predicting the

TABLE III. Values of the input parameters in the quantum reactive scattering calculations by the ABC code.

Parameter Jtotmax kmax emax (eV) jmax mtr rmax (bohrs)

Value 50 5 2.4 25 180 16.0

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 024303-6 Chen, Sun, and Zhang
FIG. 3. (a) The total reaction probabilities in low collision energy region for
the F + HD → HF + D reaction with the total angular momentum J = 0
obtained on the SW, XXZ, FXZ, and CSZ PES. (b) Same as in panel (a), but
for the F + HD → DF + H reaction.
DF reaction rate constant and success for predicting the HF
reaction rate constant, to the inaccuracy of the width and
height of the barrier. With increasing accuracy of the PES
around the transition state, the CSZ PES does not alter this
trend. As we know, the van der Waals well in the reactant
channel can influence the branching ratio of product HF/DF
substantially.62–65 On the other hand, the coupled cluster
method is unable to describe the reactant channels with the
same accurate level as for the product channel using limited
electronic excitations.
Therefore, assuming that the experimental measurements
are accurate, the failure of the CSZ PES for accurately
predicting the reactivity of the DF channel, may be largely
due to the inaccuracy around the van der Waals region in the
reactant channel. Deeper van der Waals well in the angular
degree of freedom favours the product of DF at low collision
energy,62–65 which may suggest that the van der Waals well
in the reactant channel of the CSZ PES is too shallow. This
issue is illustrated clearly in Fig. 6, where the potential energy
curves in the reactant channel as a function of RHH–F in T-shape
configurations (right panel) and r H–F in collinear configurations
(left panel) are shown, which were calculated by using the
MRCI method with reference to CASSCF functions, with a
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J. Chem. Phys. 142, 024303 (2015)
FIG. 4. Comparison of experimental and calculated integral cross sections.
The symbols are the experimental results by Liu and his coworkers (full and
open dots for the HF and DF channels, respectively).17 The curves are the ICS
calculated by including contributions of the reactants rotational state j 0 = 0
and j0 = 1, which are experimentally given as 82% and 18%, respectively,
on the two PESs (red lines: the FXZ PES and blue lines: the CSZ PES). The
theoretical ICS are translationally averaged on the experimental conditions of
the molecular beam.
relative small basis of AVTZ and a fixed bond length of r H−H.
The spin-orbit coupling is excluded. The CCSD method only
gives the results corresponding to the lines with symbols.
As shown by Alexander et al., the amplitude of the
nonadiabatic coupling is very small in this reaction, the
reaction F + H2 starting from the ground spin-orbit state
proceeds mainly along with the diabatic 2Σ1/2 potential energy
surface.48 Since the CCSD method only is capable of giving
the lowest adiabatic electronic energy, there is no problem
for calculating the surface around van der Waals well where F
comes in perpendicularly with the bond of hydrogen molecule,
since the 2Σ1/2 electronic state always has the lowest energy
around this region, as shown in the right panel of Fig. 6.
However, around the region where the three atoms have
collinear geometries in the reactant channel, the CCSD method
gives the energies which does not always follow the 2Σ1/2
electronic state, as indicated by the line with symbols in the left
panel of Fig. 6, since the 2Σ1/2 electronic state is not always the
lowest one. This fact suggests the van der Waals well calculated
by the CCSD method is shallower in the angular degree of
freedom than it should be and it unfavours the product of DF
at low collision energy. In the future work for refining the CSZ
 024303-7 Chen, Sun, and Zhang
FIG. 5. Arrhenius plots (logarithm of the rate constant versus inverse tem-
perature) for the F + HD reaction. Dots with error bars: experimental data by
Persky and Kornweitz (Refs. 52 and 61); red lines: the FXZ PES; blue lines:
the CSZ PES; dotted lines: the SW PES. Upper panel: the HF + D channel;
lower panel: the DF + H channel.
PES, we need to pay more attention to the surface around van
der Waals well in the reactant channel. With this refinement,
we may expect that the reaction rate constant of the CSZ PES
for the HF channel in the low temperature range would reduce
but the reaction rate constant for the DF channel in the low
temperature range would increase, thus the “refined” PES will
definitely give better reaction rate constants for both channels
than the FXZ PES refined in the same way.
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J. Chem. Phys. 142, 024303 (2015)
FIG. 7. Arrhenius plot (logarithm of reaction rate constants as a function of
the inverse of the temperature) for the F + n − H2 reaction, calculated by the
three typical ab initio PES comparing the available experimental results. Even
the reaction rate constants from these three ab initio PES cannot accurately
agree with the experimental measurements, the latest CSZ does agree much
better than the FXZ PES. The data for the SW PES are copied from Ref. 41
Exp. 1, Exp. 2, Exp. 3, and Exp. 4 are experimental results, which are taken
from Refs. 70–72 and Ref. 52, respectively.
In order to understand the effects of the decrease of the
barrier height of the CSZ PES in a better way, the reaction
rate constant of the F + H2 reaction calculated by the FXZ and
CSZ PES are plotted in Fig. 7, along with that of the SW
PES, comparing with the experimental results.70–72 The plots
indicate that the barrier height (1.68 kcal/mol) of the CSZ PES
is still a little higher, even which is lower than that of the FXZ
PES by 0.08 kcal/mol. Therefore, the estimated correct value
of 1.63 kcal/mol for the bent barrier should be very accurate.50
The results shown in Fig. 7 suggest that the barrier height of
the CSZ PES does approach to the realistic value closer than
that of the FXZ PES.
The backward scattering in the DCS of the reaction
F+HD → HF+D in the collision energy of 0.2 ∼ 1.4 kcal/mol
exhibits a clear peak at energy of 0.39 kcal/mol.9 The fact
that the XXZ PES predicts the corresponding peak beings
at 0.58 kcal/mol with error about 0.2 kcal/mol, leads to the
construction of the FXZ PES in the work by Ren et al.9
FIG. 6. 1D potential energy curves in
the reactant channel as a function of
R HH-F in T-shape configurations (right
panel) and r H–F in collinear configu-
rations (left panel) are calculated us-
ing the MRCI method with reference
to CASSCF functions, with a relative
small basis of AVTZ and a fixed r H−H.
The spin-orbit coupling is excluded.
The CCSD method gives the electronic
energy corresponding with the lines
with symbols, instead of always follow-
ing with the 2Σ1/2 state.
 024303-8 Chen, Sun, and Zhang
FIG. 8. Collision energy-dependent DCS for the backward scattering
HF(v ′ = 2) products summed over j ′ = 0–3. A resonance-like peak is clearly
present at the collision energy of ∼ 0.39 kcal/mol. The filled circles are the
experimental data, and the solid lines are the calculated theoretical results
based on the XXZ (yellow line), FXZ (red line), and CSZ PES (blue line).
which gives the backward scattering as a function of collision
energy fitting with the experimental measurements well. The
corresponding results calculated using the CSZ PES are plotted
in Fig. 8, compared with the experimental observations, along
with the results using the FXZ and XXZ PES. It is seen that
the CSZ PES now gives a little more accurate prediction, not
only for the position of the peak but also for the oscillations at
the higher collision energies.
The observation of the partial wave resonance in the
F + HD → HF + D reaction is a milestone in the study of the
resonance in a chemical reaction.53 Despite of the complicity
FIG. 9. Experimental and theoretical DCS of the HF(v ′ = 2, j ′ = 6) product
of the F(2P3/2) + HD ( j 0 = 0) reaction in the backward scattering direction.
The solid circles are experimental data; the real lines are the results of full
quantum dynamics calculations convoluted with the experimental resolution
and shifted 0.03 kcal/mol lower in energy for the FXZ PES (red) but without
any shifting for the CSZ PES (blue). The error bars in the experimental data
are the estimated measurement errors for the HF(v ′ = 2, j ′ = 6) product
peak intensity in the collision energy scan. The three peaks are assigned
to the partial wave Feshbach resonances of J = 12, 13, and 14 in the
F + HD → HF + D reaction.53
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J. Chem. Phys. 142, 024303 (2015)
FIG. 10. Collision energy-dependent DCS for the forward-scattering
HF(v ′ = 2) product. A resonance-like peak is clearly observed at the collision
energy of 0.52 kcal/mol. The solid circles are the experimental data, and
the solid lines are the calculated theoretical results. In panel (b), the results
obtained on the CSZ PES have been shifted upper by 0.045 kcal/mol, which
is close to the mismatch of the exothermicity (0.059 kcal/mol).
of a chemical reaction, it demonstrates that we are able to
pick up the information from a single quantum resonance
state of the intermediate complex in a reactive process. The
experimental and theoretical DCS using the CSZ and FXZ PES
of the HF(v ′ = 2, j ′ = 6) product of the F(2P3/2) + HD(j0 = 0)
reaction in the backward scattering direction are shown in
Fig. 9. We see that now without any energy shift, the CSZ
PES can reproduce the backward scattering measured by the
molecular beam experiment very well, except the result at
collision energy point of 1.42 kcal/mol. However, only with
shifting down the collision energy of 0.03 kcal/mol, the FXZ
PES can account for the observed features.
Among the three surfaces, the XXZ, FXZ, and CSZ PES,
the XXZ has highest barrier and its prediction deviates from
the experimental measurement farthest. In 2006, Qiu et al.
incidentally found that the XXZ PES was able to give accurate
position of the peak arising in the forward scattering as a
function of collision energies.7 The results predicted by the
FXZ and CSZ PES are presented in Fig. 10, compared with
the experimental measurements and the results by the XXZ
PES. Surprisingly, neither the CSZ PES nor the FXZ PES is
able to give the position of the peak accurately. By shifted
0.045 kcal/mol lower the collision energy, the CSZ PES can
reproduce the peak excellently, not only for the position but
also for the shape of the peak. This fact can be explained by
 024303-9 Chen, Sun, and Zhang
the mismatch of the exothermicity for the CSZ PES, which is
about 0.06 kcal/mol.
We also calculated the energy dependence of vibrational
branching ratios for the production of HF in selected vibra-
tional states, v ′ = 0, 1, 2, and 3. There is only negligible
difference between the calculated results using the FXZ and
CSZ PES, thus both of them can predict the energy dependence
of vibrational branching ratios for the HF channel very well.
We do not present the related plots here and one may refer Fig.
5 in Ref. 39. In passing, we note that the theoretical results
on the CSZ PES are able to reproduce the intriguing trimodal
structures in the HF(v ′ = 2, j ′) rotational distribution at the
low collision energies and rotational state distribution around
collision energy 0.19 kcal/mol of the F+H2 reaction where the
reactive resonance dominates.66
To conclude this part, experimentally measured three
dimensional polar plots of the F + HD → HF + D reaction
at collision energies of 0.31, 0.43, 0.48, 0.52, 0.59, 0.64,
and 0.71 kcal/mol are presented in Fig. 11, along with the
theoretical results calculated using the CSZ PES. The degree
of the agreement on the DCSs between experiment and theory
is remarkable. The experimental DCS varies dramatically in a
very small collision energy range in Fig. 11, and the theoretical
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J. Chem. Phys. 142, 024303 (2015)
FIG. 11. The theoretical and experi-
mental 3D polar plots for the product
translational energy and angular distri-
butions for the F(2P3/2) + HD ( j 0 = 0)
→ HF + D reaction. The theoretical
results are obtained by using the full
quantum dynamical calculations on the
current CSZ PES at various collision
energies: 0.31, 0.43, 0.48, 0.52, 0.59,
0.64, and 0.71 kcal/mol.
results obtained on the CSZ PES can reproduce closely
this dramatic variation. Anyway, the difference between the
theoretical and experimental observations does exist. The
inaccuracy of the CSZ PES definitely is responsible for the
subtle difference between the theoretical and experimental
plots. On the other hand, there is uncertainty with experimental
measurements, especially for the signals in the forward
and backward scattering direction. At the same time, the
experimental measurements only sampled at limited angles
(about 15 sample points from 0◦ to 180◦), which implied that
identical 3D polar plots between experimental and theoretical
results are difficult when there are fast oscillations in the DCS
as a function of scattering angle. This fact explains why the
experimental DCS at collision energies of 0.59, 0.64, and
0.71 kcal/mol varies as a function of the scattering angle in a
much more moderate way and do not fit with the theoretical
results so well.
IV. CONCLUSION
In summary, a three dimensional potential energy surface
for the F + H2 → HF + H reaction has been computed by the
spin unrestricted coupled cluster method with singles, doubles,
 024303-10 Chen, Sun, and Zhang
triples, and perturbative quadruples using the augmented
correlation-consistent polarised valence quadruple zeta basis
set for the fluorine atom and the correlation-consistent
polarised valence quadruple zeta basis set for the hydrogen
atom. All the calculations are based on the restricted open-shell
Hartree-Fock orbitals, together with the frozen core approxi-
mations. The UCCSD(T)/CBS correction term was included
by extrapolating UCCSD(T)/AV5Z and UCCSD(T)/AV6Z
energies. The global PES is obtained by fitting on huge ab
initio energy points using a neutral network method.
The quantum reactive scattering results on the new
surface were compared with a wide range of experimental
measurements, such as the backward scattering as a function of
collision energy, rotational states distribution, and differential
cross section at a series of collision energies of the reaction
F + HD → HF + D and F + H2, and a good agreement was
obtained. This may disclose the high accuracy of the new PES,
even the improvement over the previous FXZ PES is not so
much. Considering that the reactivity of the spin-orbit excited
state has not been taken into account in the calculations, the
agreement may be surprisingly good. On the other hand, this
fact may stress that the spin-orbit excited state plays a minor
role in this reaction.
Whereas, in view of the difference in the theoretical and
experimental thermal reaction rates and total integral cross
sections for both channels of the F + HD reaction, there is still
much room to improve for the CSZ PES. In order to refine the
CSZ PES, the regions of the CSZ surface around the van der
Waals well in the reactant channel and the transition state may
require particularly more attention.
ACKNOWLEDGMENTS
This work was supported by the National Basic Research
Program of China (No. 2013CB922200), the National Nat-
ural Science Foundation of China (Grant Nos. 21222308,
21103187, and 21133006), and the Chinese Academy of
Sciences.
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