Department of Chemistry, Columbia University, New York, New York 10027, USA.
J Chem Phys. 2010 Jul 21;133(3):034105. doi: 10.1063/1.3456556.
We develop and investigate an integral equation connecting the first passage time distribution of a stochastic process in the presence of an absorbing boundary condition and the corresponding Green's function in the absence of the absorbing boundary. Analytical solutions to the integral equations are obtained for three diffusion processes in time-independent potentials which have been previously investigated by other methods. The integral equation provides an alternative way to analytically solve the three diffusion-controlled reactive processes. In order to help analyze biological rupture experiments, we further investigate the numerical solutions of the integral equation for a diffusion process in a time-dependent potential. Our numerical procedure, based on the exact integral equation, avoids the adiabatic approximation used in previous analytical theories and is useful for fitting the rupture force distribution data from single-molecule pulling experiments or molecular dynamics simulation data, especially at larger pulling speeds, larger cantilever spring constants, and smaller reaction rates. Stochastic simulation results confirm the validity of our numerical procedure. We suggest combining a previous analytical theory with our integral equation approach to analyze the kinetics of force induced rupture of biomacromolecules.
我们开发并研究了一个积分方程,将存在吸收边界条件的随机过程的首次穿越时间分布与不存在吸收边界条件的相应格林函数联系起来。对于先前通过其他方法研究过的三个时不变势中的扩散过程,我们得到了积分方程的解析解。积分方程为三种扩散控制的反应过程提供了另一种解析求解的方法。为了帮助分析生物破裂实验,我们进一步研究了时变势中扩散过程的积分方程的数值解。我们的数值方法基于精确的积分方程,避免了先前分析理论中使用的绝热近似,对于拟合单分子拉伸实验或分子动力学模拟数据的破裂力分布数据非常有用,特别是在较大的拉伸速度、较大的悬臂弹簧常数和较小的反应速率下。随机模拟结果证实了我们数值方法的有效性。我们建议将先前的分析理论与我们的积分方程方法结合起来,分析生物大分子力诱导破裂的动力学。