AI 中文总结
该研究结合红外反射吸收光谱与杂化密度泛函理论，揭示开壳层分子可作为自旋轨道调控表面电子结构的灵敏探针，确定NO/UO₂(111)为相关电子结构方法的严格基准。
AI 中文摘要
开壳层分子是关联氧化物表面的高灵敏探针，因其部分占据的前沿轨道可显著放大吸附质-基底杂化的细微变化。结合红外反射吸收光谱与包含非共线磁性和自旋轨道耦合的杂化密度泛函理论，研究表明，引入自旋轨道耦合对重现吸附在UO₂(111)表面的NO的振动光谱至关重要，它可抑制NO前沿轨道与铀5f态间原本人为的过度杂化。自旋轨道耦合决定N-O伸缩振动的位置，而色散驱动的分子间相互作用则解释了其在单分子层覆盖时的非对称展宽。这些结果确立了开壳层分子作为自旋轨道调控表面电子结构的灵敏探针，并将NO/UO₂(111)确定为描述开壳层分子-表面相互作用的电子结构方法的严格基准。
英文摘要
Open-shell molecules are highly sensitive probes of correlated oxide surfaces because their partially occupied frontier orbitals strongly amplify subtle changes in adsorbate-substrate hybridization. Combining infrared reflection-absorption spectroscopy with hybrid density functional theory including non-collinear magnetism and spin-orbit coupling, we show that inclusion of spin-orbit coupling is essential to reproduce the vibrational spectrum of NO adsorbed on UO$_2$(111) by suppressing an otherwise artificial overhybridization between the NO frontier orbitals and uranium 5f states. While spin-orbit coupling determines the position of the N-O stretching and, dispersion-driven intermolecular interactions account for its asymmetric broadening at monolayer coverage. These results establish open-shell molecules as sensitive probes of spin-orbit-controlled surface electronic structure and identify NO/UO$_2$(111) as a stringent benchmark for electronic-structure methods describing open-shell molecule-surface interactions.
