The structure determination of surface species has long been a challenge because of their rich chemical heterogeneities. Modern tip-based microscopic techniques can resolve heterogeneities from their distinct electronic, geometric, and vibrational properties at the single-molecule level but with limited interpretation from each. Here, we combined scanning tunneling microscopy (STM), noncontact atomic force microscopy (AFM), and tip-enhanced Raman scattering (TERS) to characterize an assumed inactive system, pentacene on the Ag(110) surface. This enabled us to unambiguously correlate the structural and chemical heterogeneities of three pentacene-derivative species through specific carbon-hydrogen bond breaking. The joint STM-AFM-TERS strategy provides a comprehensive solution for determining chemical structures that are widely present in surface catalysis, on-surface synthesis, and two-dimensional materials.

表面物种的结构确定长期以来一直是一个挑战，因为它们具有丰富的化学异质性。现代的基于尖端的显微技术可以在单分子水平上通过其独特的电子，几何和振动特性来解决异质性，但每种方法的解释都有限。在这里，我们结合了扫描隧道显微镜（STM），非接触原子力显微镜（AFM）和尖端增强拉曼散射（TERS）来表征假定的非活性体系，即Ag（110）表面上的并五苯。这使我们能够通过特定的碳氢键断裂，明确关联三种并五苯衍生物的结构和化学异质性。