Non-covalently bound aromatic systems are ubiquitous and govern the physicochemical properties of various organic materials. They are important to many phenomena of biological and technological relevance, such as protein folding, base-pair stacking in nucleic acids, molecular recognition and self-assembly, DNA–drug interactions, crystal engineering and organic electronics. Nevertheless, their molecular dynamics and chemical reactivity, particularly in electronic excited states, are not fully understood. Here, we observe intermolecular Coulombic decay in benzene dimers, (C6H6)2—the simplest prototypes of noncovalent π–π interactions between aromatic systems. Intermolecular Coulombic decay is initiated by a carbon 2s vacancy state produced by electron-impact ionization and proceeds through ultrafast energy transfer between the benzene molecules. As a result, the dimer relaxes with the emission of a further low-energy electron (<10 eV) and a pair of C6H6+ cations undergoing Coulomb explosion. Coincident fragment-ion and electron momentum spectroscopy, accompanied by ab initio calculations, enables us to elucidate the dynamical details of this ultrafast relaxation process.
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Triple ionization and fragmentation of benzene trimers following ultrafast intermolecular Coulombic decay
Nature Communications Open Access 10 September 2022
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This work was jointly supported by the National Natural Science Foundation of China under grants no. 11974272 (X.R., Z.X., J.Z.) and no. 11774281 (X.R., J.Z.) and the Deutsche Forschungsgemeinschaft under project no. RE 2966/5-1 (X.R., A.D.). E.W. acknowledges a fellowship from the Alexander von Humboldt Foundation. J.Z. is grateful for support from the China Scholarship Council.
The authors declare no competing interests.
Peer review information Nature Chemistry thanks Elke Fasshauer and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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From top to bottom rows, the spectra correspond to the results for T-shape (a-c), PD (d-f), TT (g-i) and S (j-l) conformers of the benzene dimer, respectively. Left column: Total kinetic energy of all atoms (black lines) and the COM kinetic energy of the exploding C6H6+ + C6H6+ ion pair (red lines) as a function of propagation time; Middle column: The initial Coulomb energy calculated from the COM distance at t = 0 fs; Right column: Energy difference between the initial Coulomb energy and the KER.
The spectra show the measurements for a mixture of C6H6 and C6D6 (M), the pure C6H6 (H) and C6D6 (D) targets and the sum of D + H (S) result. The numbered ion mass peaks are (1) (C6H2,3)+, (2) (C6H4)+, (3) (C6H5)+, (4) (C6H6)+, (5) (13CC5H6)+, (6) (13C2C4H6)+, (7) (C6D5)+, (8) (C6D5H)+, (9) (C6D6)+, (10) (13CC5D6)+ and 11 (13C2C4D6)+. The M-S difference spectrum is obtained to estimate the possible contribution of a fusion pathway.
Supplementary Figs. 1–7, Table 1, Discussion Sections I–IV and references.
Atomic coordinates of the optimized computational models, and the initial and final configurations for molecular dynamics trajectories.
Statistical source data for Supplementary Figs. 1, 2 and 4–7.
Statistical source data for Fig. 2a,b.
Statistical source data for Fig. 3a–e.
Statistical source data for Fig. 4a–c.
Statistical source data for Fig. 5a,b.
Statistical source data for Extended Data Fig. 1.
Statistical source data for Extended Data Fig. 2.
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Ren, X., Zhou, J., Wang, E. et al. Ultrafast energy transfer between π-stacked aromatic rings upon inner-valence ionization. Nat. Chem. 14, 232–238 (2022). https://doi.org/10.1038/s41557-021-00838-4
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