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Simplified and improved string method for computing the minimum energy
paths in barrier-crossing events
Weinan Ea兲
Department of Mathematics, Princeton University, Princeton, New Jersey 08544 and PACM, Princeton
University, Princeton, New Jersey 08544
Weiqing Renb兲 and Eric Vanden-Eijndenc兲
Courant Institute of Mathematical Sciences, New York University, New York, New York 10012
共Received 22 January 2007; accepted 7 March 2007; published online 23 April 2007兲
We present a simplified and improved version of the string method, originally proposed by E et al.
关Phys. Rev. B 66, 052301 共2002兲兴 for identifying the minimum energy paths in barrier-crossing
events. In this new version, the step of projecting the potential force to the direction normal to the
string is eliminated and the full potential force is used in the evolution of the string. This not only
simplifies the numerical procedure, but also makes the method more stable and accurate. We discuss
the algorithmic details of the improved string method, analyze its stability, accuracy and efficiency,
and illustrate it via numerical examples. We also show how the string method can be combined with
the climbing image technique for the accurate calculation of saddle points and we present another
algorithm for the accurate calculation of the unstable directions at the saddle points. © 2007
American Institute of Physics. 关DOI: 10.1063/1.2720838兴
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164103-2 E, Ren, and Vanden-Eijnden J. Chem. Phys. 126, 164103 共2007兲
The basic idea of the string method is to find the MEP by In the first step, the discrete points on the string are
evolving a curve connecting a and b, under the potential evolved over some time interval ⌬t according to the full
force field. The simplest dynamics for the evolution of such potential force,
curves is given abstractly by
˙ i = − ⵜV共i兲. 共6兲
vn = − 共ⵜV兲⬜ , 共3兲 Equation 共6兲 can be integrated in time by any ODE solver,
e.g., the forward Euler method or Runge-Kutta methods, as
where vn denotes the normal velocity of the curve. We re- described in Sec. IV A.
mark that for the evolution of a curve, only the normal com- In the second step, the points are redistributed along the
ponent of the velocity matters, tangential velocity only string using a simple interpolation/reparametrization proce-
moves points along the curve, changing the parameterization dure as described in Sec. IV B.
of the curve without changing the curve itself. For the same The scheme above is not only simpler than the original
reason, when we give an explicit representation of the curve, string method 共and NEB兲, it is also more stable and more
we are free to choose any particular parameterization. The accurate, as discussed in Sec. IV C.
string method makes use of this freedom in an essential way.
To translate 共3兲 to a form that can be readily used in
numerical computations, we assume that we have picked a III. COMPARISON WITH THE NUDGED ELASTIC
particular parametrization of the curve ␥ : ␥ = 兵共␣兲 : ␣ BAND METHOD
苸 关0 , 1兴其. Then we have ˆ 共␣兲 = ␣ / 兩␣兩, where ␣ denotes the Another successful algorithm for computing the MEP is
derivative of with respect to ␣. The simplest parametriza- the NEB method.4 As the string method, NEB is a chain-of-
tion to think of is equal arc-length parametrization in which states method, since the MEP is obtained as a chain of states
␣ is a constant multiple of the arc length from a to the point connected by some spring force. The states on the chain are
共␣兲. In this case, we also have 兩␣兩 = const 共this constant viewed as different replicas of the original system.
being the length of the curve ␥兲. Even though after discretization, the string or elastic
The original form of the string method uses the follow- band are indeed represented by a chain of states, conceptu-
ing model to represent 共3兲: ally it is much more convenient to adopt a continuous view-
point as was done and expressed in 共4兲 and 共5兲. From this
˙ = − ⵜV共兲⬜ + ˆ , 共4兲 viewpoint, NEB can be thought of as an evolution upon the
elastic band method,
where ˙ denotes the time derivative of . The term ˆ
⬅ 共␣ , t兲ˆ 共␣ , t兲 is a Lagrange multiplier term added to en- ˙ = − ⵜV共兲 + ␣␣ , 共7兲
force the particular parametrization that we have chosen 共for
where is the spring constant. It is well known that the
instance, by normalized arc length兲; as explained before, this
elastic band method converges to a path that, in general, is
term does not affect the evolution of the curve itself, only its
not a MEP.11 For this reason, the nudged elastic band method
parametrization, since it does not contribute to the normal
is proposed4 which takes the form
velocity of the curve. In the actual numerical algorithm, the
action of ˆ is realized by a simple interpolation step, as we ˙ = − ⵜV共兲⬜ + 共␣␣, ˆ 兲ˆ . 共8兲
discuss below.
Compared with 共4兲, we see that the difference between the
It is easy to see that the stationary states of this dynamics
original version of the string method and the NEB is in the
共when the time derivative vanishes兲 satisfies 共2兲.
second term at the right hand side, which is there to prevent
The main difficulty with this model is in the computation
the images along the path from falling into the local minima
of the projected force. Numerical stability requires changing
at the ends, due to the potential force. In the elastic band
the way that the tangent vector is computed before and after
method, this is done by adding some artificial spring force
the saddle points are crossed.7–9 This step lowers the accu-
along the path. In the string method, this is done by enforc-
racy of the overall method.14 This projection step is elimi-
ing a particular parametrization. From an algorithmic view-
nated in the new method, which amounts to solving
point, the first approach amounts to penalizing the breaking
away images. The second approach uses interpolation to fill
˙ = − ⵜV共兲 + ¯ˆ , 共5兲 up the space created along the string due the effect of the
potential force.
where ¯共␣ , t兲ˆ 共␣ , t兲 is again a Lagrange multiplier term for The new string method takes away the projection of the
the purpose of enforcing the particular parametrization of the potential force. Clearly this idea can also be used for the
string. Clearly, 共5兲 is equivalent to 共4兲 with the identification elastic band method, i.e., we may replace 共8兲 by
¯ = + 共ⵜV , ˆ 兲, but the representation 共5兲 is better for numeri-
˙ = − ⵜV共兲 + 共␣␣, ˆ 兲ˆ . 共9兲
cal purposes
As in the original string method, in the improved method This “half-nudged” elastic band method is different from
the string is discretized into a number of images 兵i共t兲 , i both 共7兲 and 共8兲 but, like 共8兲, it has the exact MEPs as steady
= 0 , 1 , . . . , N其. The images along the string are evolved by states. Compared to 共8兲,共9兲 may also have some of the ad-
iterating upon the following two-step procedure based on vantages discussed below of the new string method over the
time splitting of the terms at the right hand side of 共5兲. original string method.
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164103-3 Simplified and improved string method J. Chem. Phys. 126, 164103 共2007兲
Finally, let us note that the string method can also be sw0 = 0, swi = si−1
w
+ Wi−共1/2兲兩쐓i − i−1
쐓
兩, i = 1,2, . . . ,N.
viewed as the inextensible limit 共 → ⬁兲 of the elastic band
method 共nudged or half nudged兲. This explains the terminol- 共13兲
ogy of “string.” Here Wi−共1/2兲 = W共Vi+1/2兲 and Vi+1/2 is the average of the po-
쐓
tential energy at i−1 and 쐓i . The weight function W共z兲 is
some positive, increasing function of z 苸 R. The mesh 兵␣쐓i 其 is
IV. ALGORITHMIC DETAILS AND PERFORMANCE obtained by normalizing 兵swi 其: ␣쐓i = swi / sNw. The new points i
OF THE NEW STRING METHOD on ␣i = i / N are then calculated by cubic spline interpolation
A. Step 1: Evolution of the images across the points 兵쐓i , i = 0 , . . . , N其 共see the Appendix兲.
Once the new points 兵n+1 i , i = 0 , . . . , N其 are calculated,
Equation 共6兲 can be integrated in time by any suitable we go back to step 1 and iterate until convergence.
ODE solver. If we denote by ni , i = 0 , . . . , N, the positions of Let us note that the above procedure of interpolation/
the images after n iterations of the scheme, the new set of reparametrization is only second order in terms of preserving
images after step 1 is given by the parameterization of the curve by arc length or energy-
쐓i = ni − ⌬t ⵜ V共ni 兲 共10兲 weighted arc length since we use linear interpolation in 共12兲
and 共13兲 to compute the length of the curve. However, the
if the forward Euler method is used, or procedure is fourth order in terms of the accuracy of the
k共1兲
i = ⌬t ⵜ V共i 兲,
n curve since we use cubic spline for the interpolation. This is
fine since we care mostly about finding the MEP accurately.
i = ⌬t ⵜ V共 i + 2 ki 兲 ,
k共2兲 n 1 共1兲
共1兲 Simplicity.
쐓i = ni − 1 共1兲 1 共2兲 1 共3兲 1 共4兲 共2兲 Better stability, which means larger time steps can be
6 ki − 3 ki − 3 ki − 6 ki
used to evolve the string. Even though the dynamics of
if the fourth order Runge-Kutta method is used. the string is artificial, this means that we can march to
the stationary states, the MEPs, faster using larger time
steps. The new string method is stable provided only
B. Step 2: Interpolation/reparametrization the time step ⌬t used in 共10兲 or 共11兲 is within the sta-
of the string bility region of the ODE solver, which is determined by
the stiffness of the potential energy V but is indepen-
Parametrization by equal arc length. In the simplest case
dent of N. In contrast, in the original string method or
when we choose to enforce the equal arc-length parametri-
the NEB method, stability imposes an additional con-
zation, the problem is simply the following: Given the values
straint on the size of the time step 共the Courant-
兵*i 其 on a nonuniform mesh 兵␣*i 其, we would like to interpo-
Friedricks-Lewy condition12兲, which gives ⌬t ⬍ C / N in
late these values onto a uniform mesh with the same number
the original string method, and ⌬t 艋 C / N2 in NEB,
of points. This is done in the following two simple steps,
where C is some constant.
with a cost of O共N兲:
共3兲 Better accuracy as a function of the number of points
共1兲 We calculate the arc length corresponding to the current along the string. The new method does not involve
images, computation of the tangent vector explicitly. This
s0 = 0, si = si−1 + 兩쐓i − i−1
쐓
兩, i = 1,2, . . . ,N. 共12兲 avoids the up-winding techniques used in the original
string method,9 which was the bottleneck for improving
The mesh 兵␣쐓i 其 is then obtained by normalizing 兵si其, its accuracy. If cubic splines are used for the interpola-
tion, and the time step is chosen appropriately, then the
␣쐓i = si/sN .
overall accuracy is fourth order, by which we mean that
共2兲 Next we use interpolation to obtain the new points n+1 i the distance between the converged string 共i.e., the
at the uniform grid points ␣i = i / N. This can be done, curve interpolated through the images 兵ni , i = 0 , . . . , N其
for example, by using cubic spline interpolation for the after convergence兲 and the MEP scales as O共N−4兲.
data 兵共␣쐓i , 쐓i 兲 , i = 0 , . . . , N其 共see the Appendix兲.
To understand the accuracy of the method, note first that
Parameterization by energy-weighted arc length. Com- the new string method converges to a state such that the
pared to equal arc-length parameterization, the energy- images ni lead to a new set of images 쐓i via time evolution
weighted arc length parameterization gives finer resolution 共step 1兲 which then lead back to the same set of images ni
around the saddle points, and thus better estimate of the en- ⬅ n+1
i after interpolation and reparametrization 共step 2兲. If
ergy barrier and also the unstable direction at those points. In there were no numerical errors, both the images ni ⬅ n+1 i
the reparametrization step, we first calculate the energy- and 쐓i would belong exactly to the MEP since the solution
weighted arc length corresponding to the current images, of 共6兲 stays on the MEP if its starts on the MEP. In practice,
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164103-4 E, Ren, and Vanden-Eijnden J. Chem. Phys. 126, 164103 共2007兲
Downloaded 01 May 2007 to 216.165.95.5. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
164103-5 Simplified and improved string method J. Chem. Phys. 126, 164103 共2007兲
calculation of tangent vectors, which is only first order accu- ing images. This can be easily achieved by using the
rate. The error in NEB scales as N−1 as well. following mesh instead of the uniform one at reparametriza-
tion:
V. CALCULATION OF SADDLE POINTS ␣0 = 0, ␣i = ␣i−1 + hi, i = 1,2, . . . ,N, 共24兲
AND UNSTABLE DIRECTIONS
再 冎
curately the whole MEP. In many cases, we are not interested
in the whole MEP, we are only interested in the saddle point ␣i쐓s/is , if i 艋 is
hi = 共25兲
and some local quantities at the saddle point for the compu- 共1 − ␣i쐓s兲/共N − is兲, if i ⬎ is .
tation of the transition rates. We will show in this section that
for this purpose, the climbing image technique developed in
Here is is the index of the climbing image, ␣i쐓 is the normal-
Ref. 6 can be naturally and easily adapted to the string s
ized arc length corresponding to the climbing image, i.e.,
method. This will allow us to identify the saddle point s to
s = 共␣i쐓 兲. The choice of ␣i’s in 共24兲 and 共25兲 amounts to
arbitrary precision at a cost of moving a single image. We s
will then describe a technique in Sec. V B for identifying splitting the string into the two pieces on each side the climb-
afterwards the unstable direction ˆ s at a cost of moving two ing image and treating the two pieces independently. The
images. discrete points on both pieces are redistributed evenly using
cubic spline interpolations.
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164103-6 E, Ren, and Vanden-Eijnden J. Chem. Phys. 126, 164103 共2007兲
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164103-7 Simplified and improved string method J. Chem. Phys. 126, 164103 共2007兲
ACKNOWLEDGMENTS
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164103-8 E, Ren, and Vanden-Eijnden J. Chem. Phys. 126, 164103 共2007兲
The equations in 共A2兲 and the two conditions at the end string in order that the scheme for integrating 共4兲 be stable. This amounts,
e.g., to using the following:
points form N linear equations for the N unknowns i. This
冦 冧
linear system is symmetric and tridiagonal and can be solved i+1 − i
, if V共i+1兲 ⬎ V共i兲 ⬎ V共i−1兲
easily by forward and backward substitutions.15 兩i+1 − i兩
i − i−1
, if V共i+1兲 ⬍ V共i兲 ⬍ V共i−1兲
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