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

Research output: Contribution to journalArticle

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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Dimethylformamide
Vacuum
Amides
Photoelectron Spectroscopy
Amines
Lasers
dimethylacetamide
formamide

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Larsen, M. A. B., Sølling, T. I., Forbes, R., Boguslavskiy, A. E., Makhija, V., Veyrinas, K., ... 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
Larsen, Martin A. B. ; Sølling, Theis I. ; Forbes, Ruaridh ; Boguslavskiy, Andrey E. ; Makhija, Varun ; Veyrinas, Kévin ; Lausten, Rune ; Stolow, Albert ; Zawadzki, Magdalena M. ; Saalbach, Lisa ; Kotsina, Nikoleta ; Paterson, Martin J. ; Townsend, Dave. / Vacuum ultraviolet excited state dynamics of small amides. In: The Journal of Chemical Physics. 2019 ; Vol. 150, No. 5.
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Larsen, MAB, Sølling, TI, Forbes, R, Boguslavskiy, AE, Makhija, V, Veyrinas, K, Lausten, R, Stolow, A, Zawadzki, MM, Saalbach, L, Kotsina, N, Paterson, MJ & Townsend, D 2019, 'Vacuum ultraviolet excited state dynamics of small amides', The Journal of Chemical Physics, vol. 150, no. 5, 054301. https://doi.org/10.1063/1.5079721

Vacuum ultraviolet excited state dynamics of small amides. / Larsen, Martin A. B.; Sølling, Theis I.; Forbes, Ruaridh; Boguslavskiy, Andrey E.; Makhija, Varun; Veyrinas, Kévin; Lausten, Rune; Stolow, Albert; Zawadzki, Magdalena M.; Saalbach, Lisa; Kotsina, Nikoleta; Paterson, Martin J.; Townsend, Dave.

In: The Journal of Chemical Physics, Vol. 150, No. 5, 054301, 07.02.2019.

Research output: Contribution to journalArticle

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AU - Larsen, Martin A. B.

AU - Sølling, Theis I.

AU - Forbes, Ruaridh

AU - Boguslavskiy, Andrey E.

AU - Makhija, Varun

AU - Veyrinas, Kévin

AU - Lausten, Rune

AU - Stolow, Albert

AU - Zawadzki, Magdalena M.

AU - Saalbach, Lisa

AU - Kotsina, Nikoleta

AU - Paterson, Martin J.

AU - Townsend, Dave

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AB - 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.

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Larsen MAB, Sølling TI, Forbes R, Boguslavskiy AE, Makhija V, Veyrinas K et al. Vacuum ultraviolet excited state dynamics of small amides. The Journal of Chemical Physics. 2019 Feb 7;150(5). 054301. https://doi.org/10.1063/1.5079721