Directly contrasting ultrafast excited-state dynamics in the gas and liquid phases is crucial to understanding the influence of complex environments. Previous studies have often relied on different spectroscopic observables, rendering direct comparisons challenging. Here, we apply extreme-ultraviolet time-resolved photoelectron spectroscopy to both gaseous and liquid cis-stilbene, revealing the coupled electronic and nuclear dynamics that underlie its isomerization. Our measurements track the excited-state wave packets from excitation along the complete reaction path to the final products. We observe coherent excited-state vibrational dynamics in both phases of matter that persist to the final products, enabling the characterization of the branching space of the S1–S0 conical intersection. We observe a systematic lengthening of the relaxation timescales in the liquid phase and a red shift of the measured excited-state frequencies that is most pronounced for the complex reaction coordinate. These results characterize in detail the influence of the liquid environment on both electronic and structural dynamics during a complete photochemical transformation.
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We thank T. Martinez, H. Weir and M. Williams for discussions and for providing the data shown in Supplementary Fig. 7a. We acknowledge financial support from ETH Zürich and the Swiss National Science Foundation through grant 200021_172946 (H.J.W.). Z.Y. acknowledges financial support from an ETH Career Seed Grant No SEED-12 19-1/1-004952-000. C.W. additionally acknowledges support from the National Natural Science Foundation of China (Grant Nos 11534004, 11627807, 11774130) and the financial support from Jilin University. J.S. and P.S. are grateful for the financial support of the Czech Science Foundation (Grant No. 21-26601X, EXPRO project). J.S. is a student of the International Max Planck Research School ‘Many-Particle Systems in Structured Environments’.
The authors declare no competing interests.
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Wang, C., Waters, M.D.J., Zhang, P. et al. Different timescales during ultrafast stilbene isomerization in the gas and liquid phases revealed using time-resolved photoelectron spectroscopy. Nat. Chem. 14, 1126–1132 (2022). https://doi.org/10.1038/s41557-022-01012-0