Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulationsElectronic supplementary information (ESI) available. See DOI: 10.1039/c4cp00977k
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 c...
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Language | English |
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Abstract | 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.
Time-resolved photoelectron spectroscopy and
ab initio
multiple spawning dynamical simulations of hexamethylcyclopentadiene reveal wavepacket evolution in a distinct degree of freedom. |
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AbstractList | 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.
Time-resolved photoelectron spectroscopy and
ab initio
multiple spawning dynamical simulations of hexamethylcyclopentadiene reveal wavepacket evolution in a distinct degree of freedom. |
Author | Wolf, T. J. A Kuhlman, T. S Unterreiner, A.-N Schalk, O Stolow, A Møller, K. B Martínez, T. J |
AuthorAffiliation | AlbaNova University Center Department of Chemistry Stanford University Institut für Physikalische Chemie and Center for Functional Nanostructures (CFN) Stanford PULSE Institute Technical University of Denmark National Research Council University of Ottawa Karlsruhe Institute of Technology (KIT) Department of Physics Stockholm University |
AuthorAffiliation_xml | – name: AlbaNova University Center – name: Stockholm University – name: Stanford PULSE Institute – name: Department of Chemistry – name: University of Ottawa – name: Institut für Physikalische Chemie and Center for Functional Nanostructures (CFN) – name: Department of Physics – name: National Research Council – name: Karlsruhe Institute of Technology (KIT) – name: Technical University of Denmark – name: Stanford University |
Author_xml | – sequence: 1 givenname: T. J. A surname: Wolf fullname: Wolf, T. J. A – sequence: 2 givenname: T. S surname: Kuhlman fullname: Kuhlman, T. S – sequence: 3 givenname: O surname: Schalk fullname: Schalk, O – sequence: 4 givenname: T. J surname: Martínez fullname: Martínez, T. J – sequence: 5 givenname: K. B surname: Møller fullname: Møller, K. B – sequence: 6 givenname: A surname: Stolow fullname: Stolow, A – sequence: 7 givenname: A.-N surname: Unterreiner fullname: Unterreiner, A.-N |
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Title | Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulationsElectronic supplementary information (ESI) available. See DOI: 10.1039/c4cp00977k |
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