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Imaging of the charge-transfer reaction of spin–orbit state-selected Ar+(2P3/2) with N2 reveals vibrational-state-specific mechanisms

Nature Chemistry volume 15, pages 1255–1261 (2023)Cite this article

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Abstract

Charge-transfer reactions are ubiquitous and play important roles in various gaseous environments, but, despite a long history of extensive research, our understanding of their dynamics at the quantum state-to-state level is still lacking. Here we report quantum-state-resolved experiments for the paradigmatic charge-transfer reaction Ar+ + N2 → Ar + N2+ using a three-dimensional velocity-map imaging crossed-beam apparatus with the Ar+ beam prepared exclusively in the spin–orbit state 2P3/2. High-resolution scattering images show strong dependence of rotational and angular distributions on the vibrational quantum number of the N2+ product. Trajectory surface-hopping calculations, which semi-quantitatively reproduce the experimental observations, support the existence of two distinct charge-transfer mechanisms. One of these, in the dominant N2+(v′ = 1) channel, is the well-known long-distance harpooning mechanism. However, the highly rotationally excited products in the forward direction are attributed to a hard-collision glory scattering mechanism, which occurs on account of the strong attraction between the collisional partners counterbalanced by the short-range repulsive interaction.

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Fig. 1: Product imaging and integrated speed distributions.
Fig. 2: Product vibrational populations.
Fig. 3: Product angular distributions.
Fig. 4: Product rotational distributions and their correlations with scattering angles.
Fig. 5: Trajectory surface-hopping calculations.

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Data availability

Data are provided with this paper and can be downloaded at https://doi.org/10.6084/m9.figshare.22821377. Source data are provided with this paper.

Code availability

The ANT program is from the Donald G. Truhlar group and can be downloaded from https://comp.chem.umn.edu/ant/.

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Acknowledgements

This work was funded by Beijing Municipal Natural Science Foundation (grant no. 1222033 to H. Gao) and Air Force Office of Scientific Research (FA9550-22-1-0350 to H. Guo). H. Gao is also supported by the Program for Young Outstanding Scientists of the Institute of Chemistry, Chinese Academy of Science (ICCAS) and the K.C. Wong Education Foundation. The computation was performed at the Center for Advanced Research Computing (CARC) at UNM. We are very grateful to D. Cappelletti for sharing the PESs with us.

Author information

Author notes

  1. Shanyu Han

    Present address: International Center for Isotope Effects Research, Nanjing University, Nanjing, China

  2. These authors contributed equally: Guodong Zhang, Dandan Lu.

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

    Guodong Zhang, Yufan Ding, Lichang Guan & Hong Gao

  2. University of Chinese Academy of Sciences, Beijing, China

    Guodong Zhang, Yufan Ding, Lichang Guan & Hong Gao

  3. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, USA

    Dandan Lu, Shanyu Han & Hua Guo

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  1. Guodong Zhang
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Contributions

The experiments were conceived and supervised by H. Gao, and carried out by G.Z. and L.G. Experimental data analysis was performed by G.Z. and Y.D. Theoretical calculations were conceived by H. Guo and performed by D.L. and S.H. The paper was written by H. Gao, with the theoretical sections contributed by H. Guo and D.L. All authors contributed to discussions about the results and paper.

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Correspondence to Hua Guo or Hong Gao.

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Nature Chemistry thanks Gabor Czako 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 Product imaging at lower collision energies.

The central slices cut from the experimentally collected three-dimensional N2+ product velocity distributions at the COM collision energies of (a) 1.141 eV, (b) 0.820 eV and (c) 0.631 eV, the red concentric rings labeled with numbers represent the kinematic cutoffs for the corresponding vibrational levels of N2+.

Source data

Extended Data Fig. 2 Product angular distributions at lower collision energies.

Top panels: measured N2+ product angular distributions for the vibrational levels v′=1 (blue) and 2 (red) at the COM collision energies of (a) 1.141 eV, (b) 0.820 eV and (c) 0.631 eV extracted from the scattering images; bottom panels: the corresponding theoretically calculated N2+ product angular distributions. The angular distributions of the v′=2 level are zoomed in and presented in the insets.

Source data

Extended Data Fig. 3 Product rotational distributions and their correlations with the scattering angles at lower collision energies.

Calculated N2+ product rotational population distributions in the vibrational levels v′=1 (black) and 2 (red) at the COM collision energies of (a) 1.141 eV, (d) 0.820 eV and (g) 0.631 eV with the population of v′=2 multiplied by a factor of 10; the corresponding correlation contour maps between the N2+ product rotational population and the scattering angle for v′=1 are shown in (b), (e) and (h), respectively; the corresponding correlation contour maps between the N2+ product rotational population and the scattering angle for v′=2 are shown in (c), (f) and (i), respectively.

Source data

Extended Data Fig. 4 Diabatic potential energy curves.

The diabatic potential energy curves are plotted along the R coordinate with r at the corresponding diatom molecule equilibrium bond lengths and collinear geometry. The three states included in our model are given in solid lines, while the two excluded are in dashed lines.

Source data

Extended Data Fig. 5 Exemplary scattering trajectories.

a–d, The trajectories for the glancing and glory scattering in the N2+(v′=1) and N2+(v′=2) channels, respectively. The parameters for these trajectories are given above the panels.

Source data

Extended Data Fig. 6 Estimation of the N2+ vibrational populations.

The top panel shows the angular ranges and the bottom panel shows the corresponding Gaussian fittings to the integrated speed distributions: (a) 0-20°; (b) 20-70°; (c) 70-180° for the COM collision energy of 1.588 eV.

Source data

Extended Data Table 1 Parameters for Morse potentials(V=De{1-exp[-β(r-re)]}^2) of N2 and N2+ species37,38
Full size table

Supplementary information

Supplementary Video 1

The trajectory for the glancing scattering in the N2+(v′ = 1) channel.

Supplementary Video 2

The trajectory for the hard-collision glory scattering in the N2+(v′ = 2) channel.

Source data

Source Data Fig. 1

Statistical source data.

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Source Data Extended Data Fig. 1

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Source Data Extended Data Fig. 5

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Source Data Extended Data Fig. 6

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Source Data Extended Data Table 1

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Zhang, G., Lu, D., Ding, Y. et al. Imaging of the charge-transfer reaction of spin–orbit state-selected Ar+(2P3/2) with N2 reveals vibrational-state-specific mechanisms. Nat. Chem. 15, 1255–1261 (2023). https://doi.org/10.1038/s41557-023-01278-y

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