Vibronic spectra of molecules are typically described within the Franck-Condon model. Here, we show that highly resolved vibronic spectra of large organic molecules on a single layer of ${\mathrm{MoS}}_2$ on Au(111) show spatial variations in their intensities, which cannot be captured within this picture. We explain that vibrationally mediated perturbations of the molecular wave functions need to be included into the Franck-Condon model. Our simple model calculations reproduce the experimental spectra at arbitrary position of the scanning tunneling microscope’s tip over the molecule in great detail.

中文翻译：

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超越Franck-Condon模型的隧道光谱中的振动激发机理

分子的振动光谱通常在Franck-Condon模型中描述。在这里，我们显示了单分子层上的大型有机分子的高分辨振动光谱${\mathrm{硫化钼}}_2$在Au（111）上显示的强度的空间变化无法在此图片中捕获。我们解释说，分子波函数的振动介导的扰动需要包括在Franck-Condon模型中。我们的简单模型计算非常详细地再现了扫描隧道显微镜尖端上分子上方任意位置的实验光谱。