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Disentangling the components of a multiconfigurational excited state in isolated chromophore with light-scanning-tunneling microscopy

2025/07/01 by Rodrigo Cezar de Campos Ferreira, Amandeep Sagwal, Jiří Doležal +2 · 1 voice · 2 citations
Biochemistry, Genetics and Molecular Biology · Neuroscience · Physics and Astronomy · #Advanced Fluorescence Microscopy Techniques #Photoreceptor and optogenetics research #Spectroscopy and Quantum Chemical Studies

paper · pdf · doi:10.1038/s41467-025-61296-x

openalex publication_date 2025/07/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/23

Abstract

Molecular radicals are efficient electroluminescent emitters due to the spin multiplicity of their electronic states. The excited states often exhibit a complex composition with multiple significant electronic configurations, which are essential for their optoelectronic properties but difficult to probe directly. Here we use light-scanning tunneling microscopy to investigate such an excited state by visualizing the response of a single radical molecule to a laser excitation. We observe characteristic atomic-scale spatial photocurrent patterns that can be tuned by applied bias voltage. We interpret these patterns as resulting from decay of an excited doublet state through sequential electron transfers with the tip and the substrate. The relative contributions of two dominating electronic configurations involved in this excited state are tuned by the applied voltage. This approach thus allows for disentangling the components of multiconfigurational excited states in single molecules. Excited states of molecular radicals are often composed of multiple electronic configurations. Here, the authors use light-assisted scanning tunneling microscopy to visualize these configurations through tuning of the applied voltage.

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