Resonant tip-enhanced Raman spectroscopy of a single-molecule Kondo System

0586289 - FZÚ 2025 RIV US eng J - Journal Article
de Campos Ferreira, Rodrigo Cezar - Sagwal, Amandeep - Doležal, Jiří - Canola, Sofia - Merino, P. - Neuman, Tomáš - Švec, Martin
Resonant tip-enhanced Raman spectroscopy of a single-molecule Kondo System.
ACS Nano. Roč. 18, č. 20 (2024), s. 13164-13170. ISSN 1936-0851. E-ISSN 1936-086X
R&D Projects: GA ČR(CZ) GA22-18718S; GA MŠMT LM2023051
Grant - others:AV ČR(CZ) LQ100102302; AV ČR(CZ) CSIC-24-10
Program: Prémie Lumina quaeruntur; Bilaterální spolupráce
Research Infrastructure: e-INFRA CZ - 90140
Institutional support: RVO:68378271
Keywords : TERS * resonant Raman * PTCDA * Kondo * SPM * break-junction
OECD category: Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)
Impact factor: 17.1, year: 2022
Method of publishing: Open access

Tip-enhanced Raman spectroscopy (TERS) under ultrahigh vacuum and cryogenic conditions enables exploration of the relations between the adsorption geometry, electronic state, and vibrational fingerprints of individual molecules. Here, we use the tip of a scanning probe microscope to lift a perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecule from a metal surface to bring it into an open-shell spin one-half anionic state. We reveal a correlation between the appearance of a Kondo resonance in differential conductance spectroscopy and concurrent characteristic changes captured by the TERS measurements. Through a detailed investigation of various adsorbed and tip-contacted PTCDA scenarios, we infer that the Raman scattering on suspended PTCDA is resonant with a higher excited state. Theoretical simulation of the vibrational spectra enables a precise assignment of the individual TERS peaks to high-symmetry Ag modes, including the fingerprints of the observed spin state.
Permanent Link: https://hdl.handle.net/11104/0353850