Revealing Intramolecular Isotope Effects with Chemical-Bond Precision.

Isotope substitution of a molecule not only changes its vibrational frequencies but also changes its vibrational distributions in real-space. Quantitatively measuring the isotope effects inside a polyatomic molecule requires both energy and spatial resolutions at the single-bond level, which has been a long-lasting challenge in macroscopic techniques. By achieving ångström resolution in tip-enhanced Raman spectroscopy (TERS), we record the corresponding local vibrational modes of pentacene and its fully deuterated form, enabling us to identify and measure the isotope effect of each vibrational mode. The measured frequency ratio ν/ν varies from 1.02 to 1.33 in different vibrational modes, indicating different isotopic contributions of H/D atoms, which can be distinguished from TERS maps in real-space and well described by the potential energy distribution simulations. Our study demonstrates that TERS can serve as a non-destructive and highly sensitive methodology for isotope detection and recognition with chemical-bond precision.