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Diradical character dependence of third-harmonic generation spectra in open-shell singlet systems

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Abstract

Using a two-site valence configuration interaction model, we reveal the diradical character (y) dependences of the third-harmonic generation (THG) spectra of singlet diradicaloids, which are described by the photon energy-dependent THG second hyperpolarizabilities γ. We particularly examine three- and two-photon resonance peaks associated with the dipole-allowed transition to the first excited state and with the dipole-forbidden transition to the second excited state, respectively. When increasing y, both peaks move to lower-energy region and become close to each other. Although the THG γ spectral intensities show resonance enhancements for any y value, we observe for THG γ the same bell-shape behavior as a function of y, as for the static γ, irrespective of the photon energy.

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Acknowledgments

This work is supported by a Grant-in-Aid for Bilateral Programs Joint Research Projects (JSPS—F.R.S.-FNRS), a Grant-in-Aid for Scientific Research (A) (No. 25248007) from Japan Society for the Promotion of Science (JSPS), a Grant-in-Aid for Scientific Research on Innovative Areas “Stimuli-responsive Chemical Species” (No. A24109002a) and “Photosynergetics” (No. A26107004a), MEXT, the Strategic Programs for Innovative Research (SPIRE), MEXT, and the Computational Materials Science Initiative (CMSI), Japan. It is also supported by the Academy Louvain (ARC “Extended π-Conjugated Molecular Tinkertoys for Optoelectronics, and Spintronics”) and by the Belgian Government (IUAP No. P7/05 “Functional Supramolecular Systems”). Theoretical calculations are partly performed using Research Center for Computational Science, Okazaki, Japan.

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Authors and Affiliations

  1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan

    Masayoshi Nakano

  2. Laboratoire de Chimie Théorique, University of Namur, rue de Bruxelles, 61, 5000, Namur, Belgium

    Benoît Champagne

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  1. Masayoshi Nakano
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  2. Benoît Champagne
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Correspondence to Masayoshi Nakano.

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Nakano, M., Champagne, B. Diradical character dependence of third-harmonic generation spectra in open-shell singlet systems. Theor Chem Acc 134, 23 (2015). https://doi.org/10.1007/s00214-015-1618-6

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