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Ultrafast energy transfer between π-stacked aromatic rings upon inner-valence ionization

Abstract

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 ππ 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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Fig. 1: Schematics of ICD in the benzene dimer illustrating subsequent electronic transitions and spatial structures of the dimer.
Fig. 2: Measured correlation map between two fragment ions from (C6H6)2 dimers.
Fig. 3: KER spectra.
Fig. 4: Scattered projectile and ejected electron spectra.
Fig. 5: Fragment-ion measurements using a mixed C6H6 and C6D6 target.

Data availability

Source data are provided with this paper. The data supporting this study are also available from the corresponding author upon reasonable request.

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Acknowledgements

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.

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Contributions

X.R. and A.D. conceived and supervised the project. X.R. performed the experiments and analysed the data. X.R., J.Z. and E.W. carried out the molecular dynamics simulations. N.S. performed the energetic calculations. X.R. and A.D. wrote the first draft of the manuscript. All authors including T.Y., Z.X. and T.P. contributed to the interpretation of the data and commented on the manuscript.

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Correspondence to Xueguang Ren.

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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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Extended data

Extended Data Fig. 1 Calculated kinetic energy spectra for C6H6+ + C6H6+ Coulomb explosion process.

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.

Source data

Extended Data Fig. 2 Measured ion TOF spectra for different targets.

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.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–7, Table 1, Discussion Sections I–IV and references.

Supplementary Data 1

Atomic coordinates of the optimized computational models, and the initial and final configurations for molecular dynamics trajectories.

Supplementary Data 2

Statistical source data for Supplementary Figs. 1, 2 and 4–7.

Source data

Source Data Fig. 2

Statistical source data for Fig. 2a,b.

Source Data Fig. 3

Statistical source data for Fig. 3a–e.

Source Data Fig. 4

Statistical source data for Fig. 4a–c.

Source Data Fig. 5

Statistical source data for Fig. 5a,b.

Source Data Extended Data Fig. 1

Statistical source data for Extended Data Fig. 1.

Source Data Extended Data Fig. 2

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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