Advanced
Fundamental Function for the Random Walk Simulation under the External Field in One Dimension
Fundamental Function for the Random Walk Simulation under the External Field in One Dimension
Bulletin of the Korean Chemical Society. 2014. Oct, 35(10): 3089-3091
Copyright © 2014, Korea Chemical Society
  • Received : April 02, 2014
  • Accepted : June 04, 2014
  • Published : October 20, 2014
Download
PDF
e-PUB
PubReader
PPT
Export by style
Article
Author
Metrics
Cited by
TagCloud
About the Authors
Joung-Hahn Yoon
Hyojoon Kim
Department of Chemistry, Dong-A University, Busan 604-714, Korea.

Abstract
Keywords
Exact Solutions in One Dimension
Firstly, we consider the random walk model without a reactive trap. Let PN ( x , n ; x 0 ) be the non-reactive probability that the walker is observed at x after n steps with the starting position x 0 on the one-dimensional lattice. Suppose that jumps to the left and to the right occur with probability p and q = 1− p , respectively. Then, the probability that the walker moved k times to the left and n k times to the right is given by the binomial distribution
PPT Slide
Lager Image
where nCk = n !/{ k !( n k )!} and k = ( x 0 + n x )/2 should be an integer satisfying − n + x 0 x n + x 0 . Unless x 0 + n x is a non-negative even number, PN is zero.
The random walk model with a single static perfect trap can be considered. This model corresponds to diffusionreaction systems with the Smoluchowski or the absorbing boundary condition. In other words, the random walker cannot escape once trapped. Let PSM ( x , n ; x 0 ) be the probability that the walker is observed at x after n steps with the starting position x 0 for the Smoluchowski boundary condition. Without loss of generality, we can assume that the trap is located at the origin and the starting position is x 0 > 0. Then, we find
PPT Slide
Lager Image
Note that n + x 0 is the maximum distance after n steps. Since
PPT Slide
Lager Image
, we have the following relation,
PPT Slide
Lager Image
This relation between PSM and PN generalizes the previous result with equal jumping probabilities. Note that PSM is zero at every other x like PN .
The survival probability SSM ( n ; x 0 ) can be obtained by summing PSM ( x , n ; x 0 ) of Eq. (3) over all possible x as
PPT Slide
Lager Image
Note that the last term comes from the summation only over 1 ≤ x n x 0 . Since PN ( x , n ; – x 0 ) = PN ( x +2 x 0 , n ; x 0 ) , Eq. (4) can be rearranged as
PPT Slide
Lager Image
Because of the property of PN , SSM ( n +1; x 0 ) = SSM ( n ; x 0 ) holds when x 0 + n is even.
Relation to the Solutions in Diffusion-influenced Reactions
As n increases, the following well-known de Moivre-Laplace theorem 19 can be used
PPT Slide
Lager Image
for k in the neighborhood of np . This theorem means that in the large n limit or in the long time limit, the discrete binomial distribution B ( n , p ) can be approximated by the normal distribution function N ( np , npq ) with the mean value np and the variance npq especially in the vicinity of k = np . Then, we obtain
PPT Slide
Lager Image
Note that this approximation is better when x x 0 = n ( q−p ), namely, Eq. (6) is better when p = q = 1/2 around x = x 0 . Since PN is zero at every other x in the discrete version, we have multiplied the factor 1/2. We can relate the parameters in the discrete version and those in the continuum version. When D is the diffusion constant, t is the time, and a is the dimensionless external field strength, we have n = 2 Dt and
PPT Slide
Lager Image
Simple computation leads to pq = 1/(2cosh a ) 2 , p/q = e 2a , and p q = tanh a . From Eq. (7), we have
PPT Slide
Lager Image
In the small field strength limit or a ≈ 0 , cosh a ≈ 1 and sinh a a , then we can reduce Eq. (9) to the well-known expression 11
PPT Slide
Lager Image
When we compare the results from Eqs. (9) and (10) with those from Eq. (1), we find that Eq. (10) usually produces results with smaller deviations than Eq. (9). This can be understood by the fact that Eq. (6) better describes the situation with a ≈ 0 . Therefore, the following approximation is found to be better in our model,
PPT Slide
Lager Image
with a = tanh −1 (2 p − 1). Then, for the PSM function of Eq. (2), we can have the known expression of 11
PPT Slide
Lager Image
The survival probability SSM ( n ; x 0 ) of Eq. (5) can be approximated by the following integral:
PPT Slide
Lager Image
where erfc( x ) is the complementary error function. The second equality comes from the substitution of (2 x n ) 2 = 2 nu 2 . If n = 2 Dt , this equation is again the same as the wellknown survival probability with the Smoluchowski boundary condition 11
PPT Slide
Lager Image
Therefore, the discrete exact solutions can be reduced to the known corresponding solutions in diffusion-influenced reactions only in the small field strength limit.
Monte Carlo Simulation Results
To confirm the present results, we perform the Monte Carlo simulations of the latticed-based random walk model. 2-6 After a particle is initially implanted at x 0 , it starts moving in random directions (one of two directions in this case) until it reaches the origin where the trap exists. Under the Smoluchowski boundary condition, the reaction always occurs when the particle moves to the trap. Therefore, when trapped, we do not have to follow the trajectory and start a new trajectory. Ten million trajectories are averaged to obtain the converged numerical results.
In Figure 1 , we plot the survival probabilities for x 0 = 2 and p = 0.55 in unit-dimensionless variables. 20 In one dimensional lattice, D = 1/2. One can confirm that Eq. (4) perfectly reproduce the simulation results. Note that a can be obtained by a = tanh −1 (2 p − 1) from Eq. (8). Therefore, we can obtain the exact results more efficiently from Eq. (4) than from simulations which have an inevitable statistical noise. It should be noted that SSM ( n + 1; x 0 ) = SSM ( n ; x 0 ) holds. One can also see that the discrete [Eq. (4)] and the continuum results [Eq. (14)] are in excellent agreement with each other. The difference between two is quantified in Figure 2 , where the deviations of Eq. (14) from Eq. (4) are compared for three conditions. For the condition of Figure 1 , the deviations reduce from approximate 3% to 1% as time goes by. For the larger x 0 and the larger p , the deviations increase as expected from the approximations of Eq. (11).
PPT Slide
Lager Image
The time-dependence of the survival probability function for x0 = 2 and p = 0.55. Closed circles are from the simulation results, which are in perfect agreement with those from Eq. (4) in the dotted line. The approximated results from Eq. (14) are plotted in the solid line.
PPT Slide
Lager Image
The time-dependent deviations of the approximated survival probability function of Eq. (14) from its discrete version of Eq. (4) for three given conditions.
In summary, the fundamental distribution functions for the lattice-based random walk model in one dimension under the influence of the external field effects are found for the nonreactive and the Smoluchowski boundary conditions. The discrete survival probability function for the Smoluchowski boundary condition is also found. Thus, the previous results 8 are generalized to include the external field effects. The numerical simulation results can be replaced by these superior analytic functions. These discrete functions are confirmed to reduce to their corresponding continuum version results only in the small field strength limit. Therefore, we have to be careful to simulate the system affected by the external field. The field effects between neighboring points should be small enough usually by decreasing the lattice constant, 20 which increases the computational cost. One important merit of this work is that we can find an optimized lattice constant by quantifying the deviations caused by the field effects.
Acknowledgements
Acknowledgments. This work was supported by research funds from Dong-A University.
References
ben-Avraham D. , Havlin S. 2000 Diffusion and Reactions in Fractals and Disordered Systems Cambridge University Press Cambridge
Kim H. , Shin S. , Lee S. , Shin K. J. 1996 J. Chem. Phys. 105 7705 -    DOI : 10.1063/1.472553
Kim H. , Shin S. , Shin K. J. 1998 J. Chem. Phys. 108 5861 -    DOI : 10.1063/1.476502
Kim H. , Shin S. , Shin K. 1998 J. Chem. Phys. Lett. 291 341 -    DOI : 10.1016/S0009-2614(98)00604-6
Kim H. , Shin K. 2000 J. Phys. Rev. E 61 3426 -    DOI : 10.1103/PhysRevE.61.3426
Kim H. 2010 Chem. Phys. Lett. 484 358 -    DOI : 10.1016/j.cplett.2009.11.033
Montroll E. W. , Weiss G. H. 1965 J. Math. Phys. 6 167 -    DOI : 10.1063/1.1704269
Yoon J. H. , Kim H. 2011 Bull. Korean Chem. Soc. 32 3521 -    DOI : 10.5012/bkcs.2011.32.9.3521
Smoluchowski M. Z. 1917 Phys. Chem. (Leipzig) 92 129 -
Chandrasekhar S. 1943 Rev. Mod. Phys. 15 1 -    DOI : 10.1103/RevModPhys.15.1
Carslaw H. S. , Jaeger J. C. 1986 Conduction of Heat in Solids 2nd ed. Oxford University Press New York
Kim H. , Shin K. J. , Agmon N. 2001 J. Chem. Phys. 114 3905 -    DOI : 10.1063/1.1344607
Kim H. , Shin K. J. 2004 J. Chem. Phys. 120 9142 -    DOI : 10.1063/1.1704632
Park S. , Shin K. J. 2006 Chem. Asian J. 1 216 -    DOI : 10.1002/asia.200600076
Park S. , Shin K. J. 2008 J. Phys. Chem. B 112 6241 -    DOI : 10.1021/jp075933x
Reigh S. Y. , Shin K. J. , Tachiya M. 2008 J. Chem. Phys. 129 234501 -    DOI : 10.1063/1.3035986
Reigh S. Y. , Shin K. J. , Kim H. 2010 J. Chem. Phys. 132 164112 -    DOI : 10.1063/1.3394894
Reigh S. Y. , Kim H. 2012 Bull. Korean Chem. Soc. 33 1015 -    DOI : 10.5012/bkcs.2012.33.3.1015
Feller W. 1968 An Introduction to Probability Theory and Its Applications 3rd ed. Wiley New York
Kim T. , Kim H. 2014 Bull. Korean Chem. Soc. 35 1209 -    DOI : 10.5012/bkcs.2014.35.4.1209