Marashdeh Ali, Saraireh Sherin A, Assaf Niveen W, Alghamdi Suzan K, Afaneh Akef T, Helal Wissam, Altarawneh Mohammednoor
Department of Chemistry, Faculty of Science, Al-Balqa Applied University Al-Salt 19117 Jordan
Physics Department, Faculty of Sciences, Taibah University Al-Madeina Al-Munawarah Saudi Arabia
RSC Adv. 2025 Aug 11;15(35):28384-28394. doi: 10.1039/d5ra02406d.
The interaction between halogen species and metal surfaces plays a crucial role in numerous surface-driven processes. The adsorption behavior and thermodynamic stability of bromine (Br) atoms on the Cu(100) surface using density functional theory (DFT) with van der Waals (vdW) corrections and atomistic thermodynamics is investigated. Surface adsorption was analyzed across three high-symmetry sites-top, bridge, and hollow-at various coverages from (0.11 to 1.00) ML. van der Waals forces significantly influence binding energy, particularly at low coverage. Hollow sites are identified as the most energetically favorable. The hollow site emerged as the most energetically favorable across most coverages, with the 0.75 ML configuration being particularly stable. Electronic density of states (DOS) analysis revealed strong Br-Cu hybridization and significant alterations in the Cu(3d) and Br(4p) states, especially at higher coverages. Thermodynamic phase diagrams demonstrated that increasing Br chemical potential leads to progressively more stable Br/Cu(100) surface configurations, shifting from clean Cu to partial and then full monolayer adsorption.
卤素物种与金属表面之间的相互作用在众多表面驱动过程中起着至关重要的作用。利用含范德华（vdW）校正的密度泛函理论（DFT）和原子热力学，研究了溴（Br）原子在Cu(100)表面的吸附行为和热力学稳定性。在(0.11至1.00) ML的各种覆盖度下，对顶位、桥位和空心位这三个高对称位点的表面吸附进行了分析。范德华力对结合能有显著影响，尤其是在低覆盖度时。空心位被确定为能量上最有利的位点。在大多数覆盖度下，空心位都是能量上最有利的，其中0.75 ML构型特别稳定。电子态密度（DOS）分析表明存在强烈的Br-Cu杂化，并且Cu(3d)和Br(4p)态有显著变化，尤其是在较高覆盖度时。热力学相图表明，增加Br化学势会导致Br/Cu(100)表面构型逐渐更稳定，从清洁的Cu表面转变为部分单层吸附，然后是完全单层吸附。
