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Probing competing r...
Probing competing relaxation pathways in malonaldehyde with transient X-ray absorption spectroscopy
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- List, Nanna H. (författare)
- Stanford Univ, Dept Chem, PULSE Inst, Stanford, CA 94305 USA.;SLAC Natl Accelerator Lab, 2575 Sand Hill Rd, Menlo Pk, CA 94025 USA.
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- Dempwolff, Adrian L. (författare)
- Heidelberg Univ, Interdisciplinary Ctr Sci Comp, Neuenheimer Feld 205, D-69120 Heidelberg, Germany.
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- Dreuw, Andreas (författare)
- Heidelberg Univ, Interdisciplinary Ctr Sci Comp, Neuenheimer Feld 205, D-69120 Heidelberg, Germany.
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- Norman, Patrick (författare)
- KTH,Teoretisk kemi och biologi
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- Martinez, Todd J. (författare)
- Stanford Univ, Dept Chem, PULSE Inst, Stanford, CA 94305 USA.;SLAC Natl Accelerator Lab, 2575 Sand Hill Rd, Menlo Pk, CA 94025 USA.
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Stanford Univ, Dept Chem, PULSE Inst, Stanford, CA 94305 USA;SLAC Natl Accelerator Lab, 2575 Sand Hill Rd, Menlo Pk, CA 94025 USA. Heidelberg Univ, Interdisciplinary Ctr Sci Comp, Neuenheimer Feld 205, D-69120 Heidelberg, Germany. (creator_code:org_t)
- 2020
- 2020
- Engelska.
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Ingår i: Chemical Science. - : Royal Society of Chemistry (RSC). - 2041-6520 .- 2041-6539. ; 11:16, s. 4180-4193
- Relaterad länk:
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https://doi.org/10.1...
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https://pubs.rsc.org...
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- Excited-state intramolecular hydrogen transfer (ESIHT) is a fundamental reaction relevant to chemistry and biology. Malonaldehyde is the simplest example of ESIHT, yet only little is known experimentally about its excited-state dynamics. Several competing relaxation pathways have been proposed, including internal conversion mediated by ESIHT and C & xe001;C torsional motion as well as intersystem crossing. We perform an in silico transient X-ray absorption spectroscopy (TRXAS) experiment at the oxygen K-edge to investigate its potential to monitor the proposed ultrafast decay pathways in malonaldehyde upon photoexcitation to its bright S-2(pi pi*) state. We employ both restricted active space perturbation theory and algebraic-diagrammatic construction for the polarization propagator along interpolated reaction coordinates as well as representative trajectories from ab initio multiple spawning simulations to compute the TRXAS signals from the lowest valence states. Our study suggests that oxygen K-edge TRXAS can distinctly fingerprint the passage through the H-transfer intersection and the concomitant population transfer to the S-1(n pi*) state. Potential intersystem crossing to T-1(pi pi*) is detectable from reappearance of the double pre-edge signature and reversed intensities. Moreover, the torsional deactivation pathway induces transient charge redistribution from the enol side towards the central C-atom and manifests itself as substantial shifts of the pre-edge features. Given the continuous advances in X-ray light sources, our study proposes an experimental route to disentangle ultrafast excited-state decay channels in this prototypical ESIHT system and provides a pathway-specific mapping of the TRXAS signal to facilitate the interpretation of future experiments.
Ämnesord
- NATURVETENSKAP -- Fysik -- Atom- och molekylfysik och optik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences -- Atom and Molecular Physics and Optics (hsv//eng)
Publikations- och innehållstyp
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