基于最佳调谐距离分离杂化泛函的分子-金属界面能级排列
Energy Level Alignment at Molecule-Metal Interfaces from an Optimally-Tuned Range-Separated Hybrid Functional
摘要：
吸附分子的前线轨道能量与金属-有机界面处的基底费米能级的对准是在纳米科学及更远的领域中具有显著实际重要性的基本观察结果。典型的密度泛函理论计算，特别是那些使用局部和半局部泛函，往往低估了水平对齐，导致不准确的电子结构和电荷输运性质。在这项工作中，我们开发了一种新的完全自洽的预测方案，以准确地计算在某些类的复杂的异质分子-金属界面的最佳调谐范围分离的混合泛函的基础上的水平对齐。从气相电子结构的高度准确的描述开始，我们的方法通过构建捕获重要的非局部表面极化效应，通过调谐的远程屏蔽交换在一个范围分离的混合在一个非经验和系统特定的方式。我们实现这一功能的平面波代码，并将其应用到几个物理吸附和化学吸附的分子-金属界面系统。我们的结果是在定量协议与实验，无论是水平对齐和功函数的变化。我们的方法构成了一个新的实用计划，准确和有效的计算分子-金属界面的电子结构。
英文摘要：
The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density functional theory calculations, especially those using local and semi-local functionals, often underestimate level alignment leading to inaccurate electronic structure and charge transport properties. In this work, we develop a new fully self-consistent predictive scheme to accurately compute level alignment at certain classes of complex heterogeneous molecule-metal interfaces based on optimally-tuned range-separated hybrid functionals. Starting from a highly accurate description of the gas-phase electronic structure, our method by construction captures important nonlocal surface polarization effects via tuning of the long-range screened exchange in a range-separated hybrid in a non-empirical and system-specific manner. We implement this functional in a plane-wave code and apply it to several physisorbed and chemisorbed molecule-metal interface systems. Our results are in quantitative agreement with experiments, both the level alignment and work function changes. Our approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.
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