School of Chemistry, Center for the Physics and Chemistry of Living Systems, Ratner Institute for Single Molecule Chemistry, and the Sackler Center for Computational Molecular and Materials Science, Tel Aviv University, 6997801 Tel Aviv, Israel.
The Institute of Mathematical Sciences, CIT Campus, Taramani, Chennai 600113, India.
J Chem Phys. 2023 Mar 7;158(9):094107. doi: 10.1063/5.0121359.
Adsorption is the accumulation of a solute at an interface that is formed between a solution and an additional gas, liquid, or solid phase. The macroscopic theory of adsorption dates back more than a century and is now well-established. Yet, despite recent advancements, a detailed and self-contained theory of single-particle adsorption is still lacking. Here, we bridge this gap by developing a microscopic theory of adsorption kinetics, from which the macroscopic properties follow directly. One of our central achievements is the derivation of the microscopic version of the seminal Ward-Tordai relation, which connects the surface and subsurface adsorbate concentrations via a universal equation that holds for arbitrary adsorption dynamics. Furthermore, we present a microscopic interpretation of the Ward-Tordai relation that, in turn, allows us to generalize it to arbitrary dimension, geometry, and initial conditions. The power of our approach is showcased on a set of hitherto unsolved adsorption problems to which we present exact analytical solutions. The framework developed herein sheds fresh light on the fundamentals of adsorption kinetics, which opens new research avenues in surface science with applications to artificial and biological sensing and to the design of nano-scale devices.
吸附是溶质在溶液和其他气相、液相或固相之间形成的界面上的积累。吸附的宏观理论可以追溯到一个多世纪以前，现在已经得到了很好的确立。然而，尽管最近取得了进展，但单颗粒吸附的详细和自成一体的理论仍然缺乏。在这里，我们通过开发吸附动力学的微观理论来弥合这一差距，宏观性质可以直接从该理论中得出。我们的一个主要成就是推导出了开创性的 Ward-Tordai 关系的微观版本，该关系通过一个适用于任意吸附动力学的通用方程将表面和次表面吸附物浓度联系起来。此外，我们还对 Ward-Tordai 关系进行了微观解释，这反过来又使我们能够将其推广到任意维度、几何形状和初始条件。我们的方法在一组迄今尚未解决的吸附问题上得到了展示，我们给出了这些问题的精确解析解。本文所发展的理论框架为吸附动力学的基本原理提供了新的视角，为表面科学的研究开辟了新的途径，可应用于人工和生物传感以及纳米级器件的设计。
