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Size-dependent optical properties of [6]-, [8]- and [10]Cycloparaphenylene dications: the role of degenerate states

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Abstract

The E \(\otimes\) e Jahn–Teller (JT) effects associated with the lowest excited degenerate electronic states (S\(_1\) and S\(_2\)) of [6]-, [8]- and [10]cycloparaphenylene dications are studied to unravel their size-dependent optical properties. A model Hamiltonian within the linear vibronic coupling approach is adapted to generate the JT-split potential energy surfaces. Computed JT stabilization energy follows the trend: [6]CPP\(^{2+}\) < [8]CPP\(^{2+}\) > [10]CPP\(^{2+}\). Theoretical absorption spectral features are generated using the wavepacket simulations within the reduced- and full-dimensional framework. These simulations reproduce the size-dependent absorption spectral broadening where the broadening increases with the increase in CPP ring size. The near-degeneracy of JT-split states (S\(_1\) and S\(_2\)) indicates a possible fluorescence emission from both the states in these molecules.

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Acknowledgements

PN thanks the Ministry of Education, Government of India, for the doctoral fellowship under Prime Minister’s Research Fellows (PMRF) scheme. The authors acknowledge IISER TVM for computational facilities.

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Authors and Affiliations

  1. Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, The Hebrew University of Jerusalem, 91904, Jerusalem, Israel

    Akhil Chakravarthy Kakarlamudi

  2. School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Maruthamala PO, Vithura, Thiruvananthapuram, 695551, India

    Probal Nag & Sivaranjana Reddy Vennapusa

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  1. Akhil Chakravarthy Kakarlamudi
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Correspondence to Sivaranjana Reddy Vennapusa.

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Details of ground-state harmonic vibrational frequencies, vibronic coupling parameters, geometries of various stationary points, and MCTDH data. (1,186 KB)

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Kakarlamudi, A.C., Nag, P. & Vennapusa, S.R. Size-dependent optical properties of [6]-, [8]- and [10]Cycloparaphenylene dications: the role of degenerate states. Theor Chem Acc 143, 31 (2024). https://doi.org/10.1007/s00214-024-03106-z

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