Structural and dynamic properties of the poly(ethylene oxide)/anatase interface (i.e., PEO/TiO₂) are explored via metadynamics simulations and density functional tight binding. 1-ns trajectories are reconstructed upon two different structure-related collective variables: interfacial Ti_surf–O_PEO distances and polymer chain torsion angles. The conformational freedom of PEO is significantly influenced by multiple favorable interactions with unsaturated Ti sites on the anatase surface. From these trajectories, several equilibrium structures extracted from the free-energy surface are analyzed using electronic structure calculations within density functional theory: the titania work function results in being largely influenced by the dynamically resolved structuring of PEO on the anatase surface. Besides the intrinsic valuable insights into the technologically relevant PEO/TiO₂ interface, our findings provide the first innovative example of an affordable yet reliable computational protocol to describe a heterogeneous interface and predict the effects of molecular dynamics on relevant physicochemical properties.

中文翻译：

---

通过第一性原理元动力学模拟阐明 PEO/（101）-TiO2 锐钛矿酶界面的结构和电子特征


通过宏动力学模拟和密度泛函紧密结合来探索聚（环氧乙烷）/锐钛矿界面（即 PEO/TiO₂）的结构和动力学特性。1 ns 轨迹在两个不同的结构相关集体变量上重建：界面 Ti_{surf-O PEO} 距离和聚合物链扭转角。PEO 的构象自由度受到与锐钛矿表面不饱和 Ti 位点的多种有利相互作用的显著影响。从这些轨迹中，使用密度泛函理论中的电子结构计算分析了从自由能表面提取的几种平衡结构：二氧化钛功函数导致在很大程度上受到锐钛矿表面 PEO 动态解析结构的影响。除了对技术相关的 PEO/TiO₂ 界面的内在有价值的见解外，我们的研究结果还提供了一个经济实惠但可靠的计算协议的创新示例，用于描述异质界面并预测分子动力学对相关物理化学性质的影响。