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Barclay MS, Quincy TJ, Williams-Young DB, et al. Accurate Assignments of Excited-State Resonance Raman Spectra: A Benchmark Study Combining Experiment and Theory. J Phys Chem A. 2017;121(41):7937-7946doi: 10.1021/acs.jpca.7b09467.
Barclay, M. S., Quincy, T. J., Williams-Young, D. B., Caricato, M., & Elles, C. G. (2017). Accurate Assignments of Excited-State Resonance Raman Spectra: A Benchmark Study Combining Experiment and Theory. The journal of physical chemistry. A, 121(41), 7937-7946. https://doi.org/10.1021/acs.jpca.7b09467
Barclay, Matthew S, et al. "Accurate Assignments of Excited-State Resonance Raman Spectra: A Benchmark Study Combining Experiment and Theory." The journal of physical chemistry. A vol. 121,41 (2017): 7937-7946. doi: https://doi.org/10.1021/acs.jpca.7b09467
Barclay MS, Quincy TJ, Williams-Young DB, Caricato M, Elles CG. Accurate Assignments of Excited-State Resonance Raman Spectra: A Benchmark Study Combining Experiment and Theory. J Phys Chem A. 2017 Oct 19;121(41):7937-7946. doi: 10.1021/acs.jpca.7b09467. Epub 2017 Oct 06. PMID: 28953391.
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J Phys Chem A. 2017 Oct 19;121(41):7937-7946. doi: 10.1021/acs.jpca.7b09467. Epub 2017 Oct 06.

Accurate Assignments of Excited-State Resonance Raman Spectra: A Benchmark Study Combining Experiment and Theory.

The journal of physical chemistry. A

Matthew S Barclay, Timothy J Quincy, David B Williams-Young, Marco Caricato, Christopher G Elles

Affiliations

  1. Department of Chemistry, University of Kansas , Lawrence, Kansas 66045, United States.
  2. Department of Chemistry, University of Washington , Seattle, Washington 98195, United States.

PMID: 28953391 DOI: 10.1021/acs.jpca.7b09467

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 on the basis of 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.

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