| Autor: |
Domingues TS; Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520, United States., Coifman RR; Department of Mathematics, Yale University, New Haven, Connecticut 06520, United States., Haji-Akbari A; Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. B [J Phys Chem B] 2023 Jun 15; Vol. 127 (23), pp. 5273-5287. Date of Electronic Publication: 2023 Jun 01. |
| DOI: |
10.1021/acs.jpcb.3c00670 |
| Abstrakt: |
Materials under confinement can possess properties that deviate considerably from their bulk counterparts. Indeed, confinement makes all physical properties position-dependent and possibly anisotropic, and characterizing such spatial variations and directionality has been an intense area of focus in experimental and computational studies of confined matter. While this task is fairly straightforward for simple mechanical observables, it is far more daunting for transport properties such as diffusivity that can only be estimated from autocorrelations of mechanical observables. For instance, there are well established methods for estimating diffusivity from experimentally observed or computationally generated trajectories in bulk systems. No rigorous generalizations of such methods, however, exist for confined systems. In this work, we present two filtered covariance estimators for computing anisotropic and position-dependent diffusivity tensors and validate them by applying them to stochastic trajectories generated according to known diffusivity profiles. These estimators can accurately capture spatial variations that span over several orders of magnitude and that assume different functional forms. Our kernel-based approach is also very robust to implementation details such as the localization function and time discretization and performs significantly better than estimators that are solely based on local covariance. Moreover, the kernel function does not have to be localized and can instead belong to a dictionary of orthogonal functions. Therefore, the proposed estimator can be readily used to obtain functional estimates of diffusivity rather than a tabulated collection of pointwise estimates. Nonetheless, the susceptibility of the proposed estimators to time discretization is higher at the immediate vicinity of hard boundaries. We demonstrate this heightened susceptibility to be common among all covariance-based estimators. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
|
