标题： 扫描隧道谱学理论超越单电子分子轨道：我们能成像分子轨道吗？ 显示英文标题

标题： Theory of scanning tunneling spectroscopy beyond one-electron molecular orbitals: can we image molecular orbitals?

摘要： 实验空间分辨扫描隧道谱（STS）图的解释通常是在单电子分子轨道的框架内进行的。 尽管这种标准做法通常能与实验数据相对吻合，但它违背了量子力学的基本假设之一，即波函数的直接观测是不可能的，也就是说，单个分子轨道无法直接观测。 扫描探针领域通常将关于观测分子轨道的这一矛盾视为一个哲学问题，而不是一个真正的难题。 此外，在多自由基强关联分子的情况下，基于单电子分子轨道的STS图解释往往失败。 因此，为了对STS图进行精确解释，并将其与分子的电子结构联系起来，需要一种理论描述，包括超越单电子过程的非平衡隧穿过程。 在本文中，我们首先说明为什么在某些情况下，基于单电子规范分子轨道和Tersoff-Hamann近似可以与实验数据达到良好的一致。 接下来，我们将展示对于强关联分子的准确解释，有必要在中性态和带电态的多电子波函数形式中描述电子的移除/添加过程。 这可以通过所谓的狄拉克轨道的概念来实现。 显示英文摘要

摘要： The interpretation of experimental spatially resolved scanning tunneling spectroscopy (STS) maps of close-shell molecules on surfaces is usually interpreted within the framework of oneelectron molecular orbitals. Although this standard practice often gives relatively good agreement with experimental data, it contradicts one of the basic assumptions of quantum mechanics, postulating the impossibility of direct observation of the wavefunction, i.e., individual molecular orbitals. The scanning probe community often considers this contradiction about observing molecular orbitals as a philosophical question rather than a genuine problem. Moreover, in the case of polyradical strongly correlated molecules, the interpretation of STS maps based on one-electron molecular orbitals often fails. Thus, for a precise interpretation of STS maps and their connection to the electronic structure of molecules, a theoretical description, including non-equilibrium tunneling processes going beyond one-electron process, is required. In this contribution, we first show why, in selected cases, it is possible to achieve good agreement with experimental data based on one-electron canonical molecular orbitals and Tersoff-Hamann approximation. Next, we will show that for an accurate interpretation of strongly correlated molecules, it is necessary to describe the process of removing/adding an electron within the formalism of many-electron wavefunctions for the neutral and charged states. This can be accomplished by the concept of so-called Dyson orbitals.