Resonance-enhanced excited-state Raman spectroscopy of conjugated thiophene derivatives: Combining experiment with theory

Barclay, Matthew S.

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https://hdl.handle.net/2142/97068 Copy

Description

Title

Resonance-enhanced excited-state Raman spectroscopy of conjugated thiophene derivatives: Combining experiment with theory

Author(s)

Barclay, Matthew S.

Contributor(s)

• Elles, Christopher G.
• Caricato, Marco
• Quincy, Timothy J.

Issue Date

2017-06-21

Keyword(s)

Multiple potential energy surfaces

Abstract

Resonance-enhanced Femtosecond Stimulated Raman Spectroscopy (FSRS) is an ultrafast experimental method that allows for the study of excited-state structural behaviors, as well as the characterization of higher electronically excited states accessible through the resonant conditions of the observed vibrations. However, interpretation of the experiment is difficult without an accurate vibrational assignment of the resonance-enhanced spectra. We therefore utilize simulations of off-resonant excited-state Raman spectra, in which we employ a numerical derivative of the analytical excited-state polarizabilities along the normal mode displacements, in order to identify and interpret the resonance-enhanced vibrations observed in experiment. We present results for a benchmark series of conjugated organic thiophene derivatives, wherein we have computed the off-resonant excited-state Raman spectra for each molecule and matched it with its resonance-enhanced experimental spectrum. This comparison allows us to successfully identify the vibrational displacements of the observed FSRS bands, as well as validate the accuracy of the theoretical results through an experimental benchmark. The agreement between the experimental and computed results demonstrates that we are able to predict qualitatively accurate excited-state Raman spectra for these conjugated thiophenes, allowing for a more thorough interpretation of excited-state Raman signals at relatively low computational cost.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Permalink

http://hdl.handle.net/2142/97068

DOI

https://doi.org/10.15278/isms.2017.WB03

Copyright and License Information

Copyright 2017 Matthew S. Barclay

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