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Optical properties of \(\hbox {Ag}_{29}\)(BDT)\(_{12}\)(TPP)\(_4\) in the VIS and UV and influence of ligand modeling based on real-time electron dynamics

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Abstract

We study the optical properties of the \(\hbox {Ag}_{29}\)(BDT)\(_{12}\)(TPP)\(_4\) cluster, the geometry of which is available from experimental structure determination, by means of Fourier-transformed induced densities from real-time (time evolution) calculations of time-dependent density-functional theory. In particular, we demonstrate the influence of the ligands on the optical spectra in the visible region and, even more, in the UV. A strong peak in the UV reminiscent of the spectrum of isolated benzene is found to be caused by the phenyl rings of the TPP ligand molecules. Nonetheless, their absence in the modeling also impacts the absorption in the visible region substantially. By contrast, the aromatic rings of the BDT ligands are more strongly coupled to the silver core and loose the character of independent oscillators; they contribute a much less peaked UV absorption. Our results underline the importance of properly accounting for the full ligands for precise and reliable modeling.

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Acknowledgements

We thank Pablo García González for enlightening discussions. This work has been carried out in part thanks to the support of the A*MIDEX grant (n\(^{\circ }\)ANR-11-IDEX-0001-02) funded by the French Government “Investissements d’Avenir” program. We acknowledge support from the French National Research Agency (Agence Nationale de Recherche, ANR) in the frame of the project “FIT SPRINGS”, ANR-14-CE08-0009. This work has used HPC resources from GENCI-IDRIS (Grant 2018-096829). Moreover, HCW and RSR would like to acknowledge the contribution of the International Research Network IRN Nanoalloys (CNRS).

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Authors and Affiliations

  1. Laboratoire des Solides Irradiés, CNRS, CEA/DRF/IRAMIS, École Polytechnique, Institut Polytechnique de Paris, 91128, Palaiseau, France

    Rajarshi Sinha-Roy

  2. Aix Marseille Univ., CNRS, CINAM, Marseille, France

    Rajarshi Sinha-Roy & Hans-Christian Weissker

  3. European Theoretical Spectroscopy Facility https://www.etsf.eu/

    Rajarshi Sinha-Roy & Hans-Christian Weissker

  4. Department of Physics and Astronomy, One UTSA Circle, The University of Texas at San Antonio, 78249-0697, San Antonio, TX, USA

    Xóchitl López-Lozano

  5. Department of Applied Physics and Materials Science, and MIRA, Northern Arizona University, Flagstaff, Arizona, 86011, USA

    Robert L. Whetten

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  1. Rajarshi Sinha-Roy
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  2. Xóchitl López-Lozano
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  3. Robert L. Whetten
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Correspondence to Hans-Christian Weissker.

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Sinha-Roy, R., López-Lozano, X., Whetten, R.L. et al. Optical properties of \(\hbox {Ag}_{29}\)(BDT)\(_{12}\)(TPP)\(_4\) in the VIS and UV and influence of ligand modeling based on real-time electron dynamics. Theor Chem Acc 140, 91 (2021). https://doi.org/10.1007/s00214-021-02783-4

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