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On the short and long phosphorescence lifetimes of aromatic carbonyls

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Abstract

This work applies theoretical and computational methods to investigate the relationship between phosphorescence lifetime and the electronic character of the lowest triplet state of aromatic carbonyls. A formal analysis of the spin-perturbed wave functions shows that phosphorescence is due to a direct spin–orbit coupling mechanism modulated by permanent dipoles when the T1 minimum is 3nπ*. If the minimum is a totally symmetric 3ππ*, phosphorescence is due to an indirect spin–orbit coupling mechanism involving transition dipole moments with other excited states. The magnitude difference between permanent and transition dipoles leads to a much faster 3nπ* phosphoresce than 3ππ*. These predictions were verified with phosphorescence lifetime simulations of benzaldehyde and its three derivatives in the gas phase employing a vertical approximation and the nuclear ensemble approaches. Both predict 3nπ* emission within a few tens of milliseconds. While the vertical approach indicates a 3ππ* emission within a few seconds, vibronic corrections bring this value down to about 200 ms.

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Data availability

The datasets generated during the current study are available in figshare repository, Ref. [62]. They include the Cartesian coordinate of stationary structures and the raw data of the NEA simulations. The NEA phosphorescence method was implemented in Newton-X and is publicly available at www.newtonx.org. PySOC is freely available at gitlab.com/light-and-molecules/pysoc.

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Acknowledgements

SM, MK, and MB thank the support of the funding provided by European Research Council (ERC) Advanced grant SubNano (Grant agreement 832237). XG thanks the National Natural Science Foundation of China, grant No. 22273122.

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Authors and Affiliations

  1. Aix Marseille University, CNRS, ICR, Marseille, France

    Saikat Mukherjee, Moumita Kar & Mario Barbatti

  2. Department of Chemistry, University of Pennsylvania, Philadelphia, PA, 19104, USA

    Mansi Bhati

  3. School of Materials, Sun Yat-Sen University, Shenzhen, 518100, Guangdong, China

    Xing Gao

  4. Institut Universitaire de France, 75231, Paris, France

    Mario Barbatti

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MB contributed to conceptualization, funding acquisition, project administration, and supervision; SM and MB carried out formal analysis, visualization, and writing—original draft; SM, MK, and MB performed investigation; XG and MB provided methodology; SM and MBh provided software; SM, MBh, XG, and MB performed writing—review and editing.

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Mukherjee, S., Kar, M., Bhati, M. et al. On the short and long phosphorescence lifetimes of aromatic carbonyls. Theor Chem Acc 142, 85 (2023). https://doi.org/10.1007/s00214-023-03020-w

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