Tepper Lucas, Dalton Benjamin, Netz Roland R
Department of Physics, Freie Universität Berlin, 14195 Berlin, Germany.
J Chem Theory Comput. 2024 Apr 23;20(8):3061-3068. doi: 10.1021/acs.jctc.3c01289. Epub 2024 Apr 11.
Memory effects emerge as a fundamental consequence of dimensionality reduction when low-dimensional observables are used to describe the dynamics of complex many-body systems. In the context of molecular dynamics (MD) data analysis, accounting for memory effects using the framework of the generalized Langevin equation (GLE) has proven efficient, accurate, and insightful, particularly when working with high-resolution time series data. However, in experimental systems, high-resolution data are often unavailable, raising questions about the impact of the data resolution on the estimated GLE parameters. This study demonstrates that direct memory extraction from time series data remains accurate when the discretization time is below the memory time. To obtain memory functions reliably, even when the discretization time exceeds the memory time, we introduce a Gaussian Process Optimization (GPO) scheme. This scheme minimizes the deviation of discretized two-point correlation functions between time series data and GLE simulations and is able to estimate accurate memory kernels as long as the discretization time stays below the longest time scale in the data, typically the barrier crossing time.
当使用低维可观测量来描述复杂多体系统的动力学时,记忆效应作为降维的一个基本结果而出现。在分子动力学(MD)数据分析的背景下,使用广义朗之万方程(GLE)框架来考虑记忆效应已被证明是高效、准确且有见地的,特别是在处理高分辨率时间序列数据时。然而,在实验系统中,高分辨率数据往往不可用,这就引发了关于数据分辨率对估计的GLE参数的影响的问题。本研究表明,当离散化时间低于记忆时间时,从时间序列数据中直接提取记忆仍然是准确的。为了可靠地获得记忆函数,即使离散化时间超过记忆时间,我们引入了一种高斯过程优化(GPO)方案。该方案使时间序列数据与GLE模拟之间离散化的两点相关函数的偏差最小化,并且只要离散化时间保持在数据中最长时间尺度以下,通常是势垒穿越时间,就能够估计准确的记忆核。