MS Barclay, TJ Quincy, DB Williams-Young, M Caricato… – The Journal of Physical …, 2017
Abstract
Femtosecond stimulated Raman scattering (FSRS) probes the structural dynamics of molecules in electronically excited states by following the evolution of the vibrational spectrum. Interpreting the dynamics requires accurate assignments to connect the vibrational bands with specific nuclear motions of an excited molecule. However, the assignment of FSRS signals is often complicated by mode-specific resonance enhancement effects that are difficult to calculate for molecules in electronically excited states. We present benchmark results for a series of eight aryl-substituted thiophene derivatives to show that calculated off-resonance Raman spectra can be used to assign experimental bands based on a comparison of structurally similar compounds and careful consideration of the resonance condition. Importantly, we show that direct comparison with the off-resonant calculations can lead to incorrect assignments of the experimental spectrum if the resonance condition is neglected. These results highlight the importance of resonance enhancement effects in assigning FSRS spectra.
… The baseline subtraction method is described in the supplemental information (SI). We record off-resonant ground-state Raman spectra using a commercial Raman spectrometer (StellarNet) Raman-HR-TEC with 785 nm laser source and 4 cm−1 resolution. …