Abstract
Electron dynamics in water are of fundamental importance for a broad range of phenomena1,2,3, but their real-time study faces numerous conceptual and methodological challenges4,5,6. Here we introduce attosecond size-resolved cluster spectroscopy and build up a molecular-level understanding of the attosecond electron dynamics in water. We measure the effect that the addition of single water molecules has on the photoionization time delays7,8,9of water clusters. We find a continuous increase of the delay for clusters containing up to four to five molecules and little change towards larger clusters. We show that these delays are proportional to the spatial extension of the created electron hole, which first increases with cluster size and then partially localizes through the onset of structural disorder that is characteristic of large clusters and bulk liquid water. These results indicate a previously unknown sensitivity of photoionization delays to electron-hole delocalization and indicate a direct link between electronic structure and attosecond photoionization dynamics. Our results offer new perspectives for studying electron-hole delocalization and its attosecond dynamics.
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Acknowledgements
We thank A. Schneider and M. Seiler for their technical support. We gratefully acknowledge funding from an European Research Council Consolidator grant (project no. 772797-ATTOLIQ), project no. 200021_172946 as well as the NCCR-MUST, funding instruments of the Swiss National Science Foundation. D.J. thanks the European Union’s Horizon 2020 programme (FP-RESOMUS – MSCA 801459) program for a fellowship and A. Schild for introduction to ORBKIT. X.G. thanks the National Natural Science Foundation of China (grant nos. 12122404 and 11974114) for financial support. Most of the theoretical results have been obtained on the ETH Zürich Euler cluster and the NCCR-Cluster supercomputer. The basis-set complex Kohn variational calculations, obtained at the Lawrence Berkeley National Laboratory (LBNL), were realized with the support of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231. Calculations performed there made use of the resources of the National Energy Research Scientific Computing Centre, a DOE Office of Science User Facility, and the Lawrencium computational cluster resource provided by the IT Division at the LBNL.
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X.G. and S.H. carried out the experiments and analysed the experimental data. X.G. constructed the experimental apparatus with contributions from S.H., K.Z. and C.P. D.J. performed most of the theoretical calculations. R.L. realized the basis-set complex Kohn variational calculations. X.G., S.H. and H.J.W wrote the initial manuscript. All authors discussed and reviewed the manuscript.
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Extended data figures and tables
Extended Data Fig. 1 Effect of the channel coupling on photoionization delays of the 1b1band.
a, Calculated time delays for photoionization out of the 1b1band of water clusters relative to H2O for a kinetic energy of eKE = 6.0 eV (SB12). The results of the single-channel calculations using ePolyScat30,31(filled circles) are compared with multi-channel calculations using the basis-set complex Kohn method32,33,34(filled triangles) are compared. The experimental results are identical to those shown in Fig.3.b, Same asa, but calculated/measured for SB14.
Extended Data Fig. 2 Effect of orbital delocalization on photoionization delays of the 3a1band.
Correlation between the photoionization delays and the first moment of the electron-hole density of the 3a1-orbital-band of water monomer and tetramer (s4) for a kinetic energy of eKE = 6 eV.
扩展数据图3分子的几何效应on orbital delocalization and photoionization delays of (H2O)4s4.
The structures are obtained from AIMD time propagation at different times (see legend). AIMD are run using density-functional theory, the Turbomole software package, the B3-LYP density functional, the def2-TZVP basis and a temperature ofT = 100 K.
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Gong, X., Heck, S., Jelovina, D.et al.Attosecond spectroscopy of size-resolved water clusters.Nature609, 507–511 (2022). https://doi.org/10.1038/s41586-022-05039-8
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DOI:https://doi.org/10.1038/s41586-022-05039-8
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