Vacuum ultraviolet excited state dynamics of small amides

Martin A. B. Larsen, Theis I. Sølling, Ruaridh Forbes, Andrey E. Boguslavskiy, Varun Makhija, Kévin Veyrinas, Rune Lausten, Albert Stolow, Magdalena M. Zawadzki, Lisa Saalbach, Nikoleta Kotsina, Martin J. Paterson, Dave Townsend

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Abstract

Time-resolved photoelectron spectroscopy in combination with ab initio quantum chemistry calculations was used to study ultrafast excited state dynamics in formamide (FOR), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA) following 160 nm excitation. The particular focus was on internal conversion processes within the excited state Rydberg manifold and on how this behavior in amides compared with previous observations in small amines. All three amides exhibited extremely rapid (<100 fs) evolution from the Franck-Condon region. We argue that this is then followed by dissociation. Our calculations indicate subtle differences in how the excited state dynamics are mediated in DMA/DMF as compared to FOR. We suggest that future studies employing longer pump laser wavelengths will be useful for discerning these differences.

Original languageEnglish
Article number054301
JournalThe Journal of Chemical Physics
Volume150
Issue number5
Early online date5 Feb 2019
DOIs
Publication statusPublished - 7 Feb 2019

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    Larsen, M. A. B., Sølling, T. I., Forbes, R., Boguslavskiy, A. E., Makhija, V., Veyrinas, K., Lausten, R., Stolow, A., Zawadzki, M. M., Saalbach, L., Kotsina, N., Paterson, M. J., & Townsend, D. (2019). Vacuum ultraviolet excited state dynamics of small amides. The Journal of Chemical Physics, 150(5), [054301]. https://doi.org/10.1063/1.5079721