Section on Molecular Transport, Eunice Kennedy Shriver National Institute of Child Health and Human Development, National Institutes of Health, Bethesda, Maryland 20892, USA.
J Chem Phys. 2017 Oct 7;147(13):134104. doi: 10.1063/1.4993129.
We study transitions of diffusing particles between the left and right ends of expanding and narrowing conical tubes. In an expanding tube, such transitions occur faster than in the narrowing tube of the same length and radius variation rate. This happens because the entropy potential pushes the particle towards the wide tube end, thus accelerating the transitions in the expanding tube and slowing them down in the narrowing tube. To gain deeper insight into how the transitions occur, we divide each trajectory into the direct-transit and looping segments. The former is the final part of the trajectory, where the particle starting from the left tube end goes to the right end without returning to the left one. The rest of the trajectory is the looping segment, where the particle, starting from the left tube end, returns to this end again and again until the direct transition happens. Our focus is on the durations of the two segments and their sum, which is the duration of the particle first passage between the left and right ends of the tube. We approach the problem using the one-dimensional description of the particle diffusion along the tube axis in terms of the modified Fick-Jacobs equation. This allows us to derive analytical expressions for the Laplace transforms of the probability densities of the first-passage, direct-transit, and looping times, which we use to find the mean values of these random variables. Our results show that the direct transits are independent of the entropy potential and occur as in free diffusion. However, this "free diffusion" occurs with the effective diffusivity entering the modified Fick-Jacobs equation, which is smaller than the particle diffusivity in a cylindrical tube. This is the only way how the varying tube geometry manifests itself in the direct transits. Since direct-transit times are direction-independent, the difference in the first-passage times in the tubes of the two types is due to the difference in the durations of the looping segments in the expanding and narrowing tubes. Obtained analytical results are supported by three-dimensional Brownian dynamics simulations.
我们研究了扩散粒子在膨胀和收缩锥形管的左右两端之间的跃迁。在膨胀管中,这种跃迁比在长度和半径变化率相同的收缩管中更快。这是因为熵势将粒子推向宽管端,从而加速了膨胀管中的跃迁,而减缓了收缩管中的跃迁。为了更深入地了解跃迁是如何发生的,我们将每个轨迹分为直接跃迁和循环段。前者是轨迹的最后一部分,其中从左管端开始的粒子在不返回左管端的情况下直接到达右管端。轨迹的其余部分是循环段,其中从左管端开始的粒子一次又一次地返回该端,直到直接跃迁发生。我们关注的是这两个段的持续时间及其总和,即粒子在管的左右两端之间首次通过的持续时间。我们使用沿管轴的粒子扩散的一维描述,即修正的 Fick-Jacobs 方程,来解决这个问题。这使我们能够为首次通过、直接跃迁和循环时间的概率密度的拉普拉斯变换导出解析表达式,我们使用这些表达式来找到这些随机变量的平均值。我们的结果表明,直接跃迁与熵势无关,并且像自由扩散一样发生。然而,这种“自由扩散”是在进入修正的 Fick-Jacobs 方程的有效扩散系数的情况下发生的,该系数小于圆柱形管中的粒子扩散系数。这是变化的管几何形状在直接跃迁中表现出来的唯一方式。由于直接跃迁时间与方向无关,因此两种类型的管中的首次通过时间的差异是由于膨胀管和收缩管中循环段的持续时间的差异所致。获得的解析结果得到了三维布朗动力学模拟的支持。