Abstract
Intermolecular Coulombic decay (ICD) is a process whereby photoexcited molecules relax by ionizing their neighbouring molecules. ICD is efficient when intermolecular interactions are active and consequently it is observed only in weakly bound systems, such as clusters and hydrogen-bonded systems. Here we report an efficient ICD between unbound molecules excited at ambient-light intensities. On the photoexcitation of gas-phase pyridine monomers, well below the ionization threshold and at low laser intensities, we detected the parent and heavier-than-parent cations. The isotropic emission of slow electrons revealed ICD as the underlying process. π–π* excitation in unbounded pyridine monomers triggered an associative interaction between them, which leads to an efficient three-centre ICD. The cation resulting from the molecular association of the three pyridine centres relaxed through fragmentation. This below-threshold ionization under ambient light has implications for the understanding of radiation damage and astrochemistry.
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Acknowledgements
This work was supported by the Department of Science and Technology through project no. EMR/2016/005247 (G.A.) and the Indian Space Research Organisation through project no. ICSR/ISRO-IITM/PHY/16-17/173/GARA (G.A. and R.K.K.).
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S.B., G.A. and Y.S. conceived the three-centre ICD mechanism. S.B. and G.A. planned the experiment and carried out the measurements with the support of S.D., N.R.B. and R.K.K. Y.S. planned the quantum-chemistry calculations. The results were discussed among the authors. Y.S. and G.A. prepared the manuscript.
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Nature Chemistry thanks Xueguang Ren and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Barik, S., Dutta, S., Behera, N.R. et al. Ambient-light-induced intermolecular Coulombic decay in unbound pyridine monomers. Nat. Chem. 14, 1098–1102 (2022). https://doi.org/10.1038/s41557-022-01002-2
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DOI: https://doi.org/10.1038/s41557-022-01002-2