Wang Shuqiao, Hensley Alyssa J R
Department of Chemical Engineering and Materials Science, Stevens Institute of Technology, Hoboken, New Jersey 07030 United States.
ACS Phys Chem Au. 2024 Apr 26;4(4):328-335. doi: 10.1021/acsphyschemau.4c00019. eCollection 2024 Jul 24.
Heterogeneous interfaces are critical in a wide range of applications, and their material properties can be tuned via changes in the coverage and configuration of chemical adsorbates. However, the tunability of such adlayers is limited by a lack of knowledge surrounding the impact of adsorbate internal structure and rotational symmetry on lateral interactions between coadsorbates. Using density functional theory (DFT) and cluster expansions, we systematically determine the impacts of rotational symmetry on lateral interactions between coadsorbates as a function of DFT functional, adsorbate type, metal type, and cluster configuration. Results indicate that the rotational symmetry effects can be nearly exclusively partitioned into the shortest 2-body clusters. By electronic analysis, the nature and strength of such effects on the lateral interactions are attributed to a balance of repulsive and attractive electrostatic interactions that are dependent on the adsorbate and metal types. Taken together, our characterization of the impacts of adsorbate internal structure and rotational symmetry on lateral interactions enables improved accuracy within multiscale modeling of multibody adsorbates at heterogeneous interfaces.
异质界面在广泛的应用中至关重要，其材料特性可通过化学吸附质覆盖度和构型的变化进行调节。然而，由于缺乏关于吸附质内部结构和旋转对称性对共吸附质之间横向相互作用影响的认识，此类吸附层的可调性受到限制。利用密度泛函理论（DFT）和团簇展开，我们系统地确定了旋转对称性作为DFT泛函、吸附质类型、金属类型和团簇构型的函数对共吸附质之间横向相互作用的影响。结果表明，旋转对称效应几乎完全可归因于最短的两体团簇。通过电子分析，此类对横向相互作用影响的性质和强度归因于依赖于吸附质和金属类型的排斥和吸引静电相互作用的平衡。综上所述，我们对吸附质内部结构和旋转对称性对横向相互作用影响的表征能够提高多相界面多体吸附质多尺度建模的准确性。
