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Hexamethylcyclopent...
Hexamethylcyclopentadiene : time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations
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Wolf, T. J. A. (författare)
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Kuhlman, T. S. (författare)
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- Schalk, Oliver (författare)
- Stockholms universitet,Fysikum
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Martinez, T. J. (författare)
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Moller, K. B. (författare)
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Stolow, A. (författare)
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Unterreiner, A. -N (författare)
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(creator_code:org_t)
- 2014
- 2014
- Engelska.
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 16:23, s. 11770-11779
- Relaterad länk:
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https://backend.orbi...
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
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- Progress in our understanding of ultrafast light-induced processes in molecules is best achieved through a close combination of experimental and theoretical approaches. Direct comparison is obtained if theory is able to directly reproduce experimental observables. Here, we present a joint approach comparing time-resolved photoelectron spectroscopy (TRPES) with ab initio multiple spawning (AIMS) simulations on the MS-MR-CASPT2 level of theory. We disentangle the relationship between two phenomena that dominate the immediate molecular response upon light absorption: a spectrally dependent delay of the photoelectron signal and an induction time prior to excited state depopulation in dynamics simulations. As a benchmark molecule, we have chosen hexamethylcyclopentadiene, which shows an unprecedentedly large spectral delay of (310 +/- 20) fs in TRPES experiments. For the dynamics simulations, methyl groups were replaced by hydrogen atoms having mass 15 and TRPES spectra were calculated. These showed an induction time of (108 +/- 10) fs which could directly be assigned to progress along a torsional mode leading to the intersection seam with the molecular ground state. In a stepladder-type approach, the close connection between the two phenomena could be elucidated, allowing for a comparison with other polyenes and supporting the general validity of this finding for their excited state dynamics. Thus, the combination of TRPES and AIMS proves to be a powerful tool for a thorough understanding of ultrafast excited state dynamics in polyenes.
Ämnesord
- NATURVETENSKAP -- Fysik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences (hsv//eng)
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