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Galiana, JoachimAuthor

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December 12, 2024
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Excitation energy transfer and vibronic relaxation through light-harvesting dendrimer building blocks: A nonadiabatic perspective

Publicated to: Journal Of Chemical Physics. 160 (10): 104104- - 2024-03-14 160(10), DOI: 10.1063/5.0193264

Authors:

Galiana, Joachim; Lasorne, Benjamin
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Affiliations

Univ Montpellier, ICGM, CNRS, ENSCM, Montpellier, France - Author

Abstract

The light-harvesting excitonic properties of poly(phenylene ethynylene) (PPE) extended dendrimers (tree-like pi-conjugated macromolecules) involve a directional cascade of local excitation energy transfer (EET) processes occurring from the "leaves" (shortest branches) to the "trunk" (longest branch), which can be viewed from a vibronic perspective as a sequence of internal conversions occurring among a connected graph of nonadiabatically coupled locally excited electronic states via conical intersections. The smallest PPE building block that is able to exhibit EET, the asymmetrically meta-substituted PPE oligomer with one acetylenic bond on one side and two parallel ones on the other side (hence, 2-ring and 3-ring para-substituted pseudo-fragments), is a prototype and the focus of the present work. From linear-response time-dependent density functional theory electronic-structure calculations of the molecule as regards its first two nonadiabatically coupled, optically active, singlet excited states, we built a (1 + 2)-state-8-dimensional vibronic-coupling Hamiltonian model for running subsequent multiconfiguration time-dependent Hartree wavepacket relaxations and propagations, yielding both steady-state absorption and emission spectra as well as real-time dynamics. The EET process from the shortest branch to the longest one occurs quite efficiently (about 80% quantum yield) within the first 25 fs after light excitation and is mediated vibrationally through acetylenic and quinoidal bond-stretching modes together with a particular role given to the central-ring anti-quinoidal rock-bending mode. Electronic and vibrational energy relaxations, together with redistributions of quantum populations and coherences, are interpreted herein through the lens of a nonadiabatic perspective, showing some interesting segregation among the foremost photoactive degrees of freedom as regards spectroscopy and reactivity.
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Keywords

Conical intersectionFunnelsLocalizatioMolecular-dynamicsSpectra

Quality index

Bibliometric impact. Analysis of the contribution and dissemination channel

The work has been published in the journal Journal Of Chemical Physics due to its progression and the good impact it has achieved in recent years, according to the agency Scopus (SJR), it has become a reference in its field. In the year of publication of the work, 2024 there are still no calculated indicators, but in 2023, it was in position , thus managing to position itself as a Q1 (Primer Cuartil), in the category Physics and Astronomy (Miscellaneous).

Independientemente del impacto esperado determinado por el canal de difusión, es importante destacar el impacto real observado de la propia aportación.

Según las diferentes agencias de indexación, el número de citas acumuladas por esta publicación hasta la fecha 2026-04-01:

  • WoS: 3
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Impact and social visibility

From the perspective of influence or social adoption, and based on metrics associated with mentions and interactions provided by agencies specializing in calculating the so-called "Alternative or Social Metrics," we can highlight as of 2026-04-01:

  • The use of this contribution in bookmarks, code forks, additions to favorite lists for recurrent reading, as well as general views, indicates that someone is using the publication as a basis for their current work. This may be a notable indicator of future more formal and academic citations. This claim is supported by the result of the "Capture" indicator, which yields a total of: 2 (PlumX).

With a more dissemination-oriented intent and targeting more general audiences, we can observe other more global scores such as:

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    Leadership analysis of institutional authors

    This work has been carried out with international collaboration, specifically with researchers from: France.

    There is a significant leadership presence as some of the institution’s authors appear as the first or last signer, detailed as follows: First Author (GALIANA, JOACHIM WALTER JOSE) .

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    Awards linked to the item

    J.G. acknowledges the French MESR (Ministere de l'Enseignement Superieur, de la Recherche) and the ENS (Ecole Normale Superieure) of Lyon for funding his Ph.D. grant, hosted at the University of Montpellier.
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