Surface-enhanced hyper-Raman scattering of Rhodamine 6G isotopologues: Assignment of lower vibrational frequencies

Jacob E. Olson, Zhongwei Hu, Michael D. Best, Lasse Jensen, Jon P. Camden

Research output: Contribution to journalArticlepeer-review

Abstract

We report a comprehensive experimental and theoretical study of the lower-wavenumber vibrational modes in the surface-enhanced hyper-Raman scattering (SEHRS) of Rhodamine 6G (R6G) and its isotopologue R6G-d4. Measurements acquired on-resonance with two different electronic states, S1 and S2, are compared to the time-dependent density functional theory computations of the resonance hyper-Raman spectra and electrodynamics-quantum mechanical computations of the SEHRS spectra on-resonance with S1 and S2. After accounting for surface orientation, we find excellent agreement between experiment and theory for both R6G and its isotopologue. We then present a detailed analysis of the complex vibronic coupling effects in R6G and the importance of surface orientation for characterizing the system. This combination of theory and experiment allows, for the first time, an unambiguous assignment of lower-wavenumber vibrational modes of R6G and its isotopologue R6G-d4.

Original languageEnglish (US)
Article number034703
JournalJournal of Chemical Physics
Volume154
Issue number3
DOIs
StatePublished - Jan 21 2021

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Surface-enhanced hyper-Raman scattering of Rhodamine 6G isotopologues: Assignment of lower vibrational frequencies'. Together they form a unique fingerprint.

Cite this