Monitoring Vibrational Evolution in Jahn-Teller Effect by Raman Imaging

The Jahn-Teller effect (JTE) reduces the geometrical symmetry of a system with degenerate electronic states via vibronic coupling, playing a pivotal role in molecular and condensed systems. In this Letter, we propose that vibrational resolved tip-enhanced Raman scattering images can visualize the vibrational evolutions in JTE in real space. Taking an experimentally viable single zinc phthalocyanine (ZnPc) molecule as a proof-of-principle example, not only the degenerate vibrational splitting but also the overlooked vibration mixing caused by the JTE in its anionic form can be straightforwardly characterized by Raman images. Leveraging Raman images, the controllable configuration of JTE distortion with partial isotopic substitution could be further identified. These findings establish a practical protocol to monitor the detailed vibrational evolutions when a single molecule experiences JTE, opening a door for visualization of spontaneous symmetry breaking in molecular and solid-state systems.