Collective Mid-Infrared Vibrations in Surface-Enhanced Raman Scattering.

ABSTRACT: Surface-enhanced Raman scattering (SERS) is typically assumed to occur at individual molecules neglecting intermolecular vibrational coupling. Here, we show instead how collective vibrations from infrared (IR) coupled dipoles are seen in SERS from molecular monolayers. Mixing IR-active molecules with IR-inactive spacer molecules controls the intermolecular separation. Intermolecular coupling leads to vibrational frequency upshifts up to 8 cm^-1, tuning with the mixing fraction and IR dipole strength, in excellent agreement with microscopic models and density functional theory. These cooperative frequency shifts can be used as a ruler to measure intermolecular distance and disorder with angstrom resolution. We demonstrate this for photochemical reactions of 4-nitrothiophenol, whic

SUBMITTER: Mueller NS 

PROVIDER: S-EPMC9479150 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature