Direct observation of collective modes coupled to molecular orbital–driven charge transfer
The making of a molecular movie
Phase transitions familiar from everyday life, such as boiling or melting, are caused by changing the temperature. In the laboratory, however, researchers can also change the phase of a material by shining intense light on it. During such transitions, changes occur in both the electronic and lattice structure of the material. Ishikawa et al. used ultrafast optical and electron diffraction probes to monitor both types of change simultaneously during a photo-induced phase transition in a molecular crystal. The resulting molecular movies showed expansion of the intermolecular distance, flattening of the molecules, and tilting of molecular dimers.
Science, this issue p. 1501
Abstract
Correlated electron systems can undergo ultrafast photoinduced phase transitions involving concerted transformations of electronic and lattice structure. Understanding these phenomena requires identifying the key structural modes that couple to the electronic states. We report the ultrafast photoresponse of the molecular crystal Me4P[Pt(dmit)2]2, which exhibits a photoinduced charge transfer similar to transitions between thermally accessible states, and demonstrate how femtosecond electron diffraction can be applied to directly observe the associated molecular motions. Even for such a complex system, the key large-amplitude modes can be identified by eye and involve a dimer expansion and a librational mode. The dynamics are consistent with the time-resolved optical study, revealing how the electronic, molecular, and lattice structures together facilitate ultrafast switching of the state.
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Supplementary Material
Summary
Materials and Methods
Figs. S1 to S24
Tables S1 to S4
Movies S1 and S2
Resources
References and Notes
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Information & Authors
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Published In
Science
Volume 350 | Issue 6267
18 December 2015
18 December 2015
Copyright
Copyright © 2015, American Association for the Advancement of Science.
Submission history
Received: 14 April 2015
Accepted: 6 November 2015
Published in print: 18 December 2015
Acknowledgments
We thank G. Sciaini and G. Moriena for help constructing the FED apparatus; W. Kazub, M. Lorenc, and A. Moreac for their help in the early stage of the optical study; and T. Tsumuraya for information concerning the band calculation. The electron diffraction work was funded by the Max Planck Society in collaboration with the Centre for Free Electron Laser Science and the Hamburg Centre for Ultrafast Imaging. This work was also partially supported by Grants-in-Aid for Scientific Research (A) (no. 15H02103) from the Ministry of Education, Culture, Supports, Science, and Technology of Japan, and CREST, JST. G.C. thanks the Alexander von Humboldt Foundation for support. M.H. acknowledges the Japan Science Technology Agency (JST), PRESTO, for funding the project “Molecular technology and creation of new functions.” The authors declare no conflicts of interest.
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