Unveiling the spatial distribution of molecular coherences at conical intersections by covariance X-ray diffraction signals

Cavaletto, Stefano M.; Keefer, Daniel; Rouxel, Jérémy R.; Aleotti, Flavia; Segatta, Francesco; Garavelli, Marco; Mukamel, Shaul

doi:10.1073/pnas.2105046118

Title: Unveiling the spatial distribution of molecular coherences at conical intersections by covariance X-ray diffraction signals

Journal Article · 28 May 2021 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.2105046118 · OSTI ID:1785155

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Department of Chemistry, University of California, Irvine, CA 92697,, Department of Physics &, Astronomy, University of California, Irvine, CA 92697,
Department of Chemistry, University of California, Irvine, CA 92697,, Department of Physics &, Astronomy, University of California, Irvine, CA 92697,, University Lyon, UJM-Saint-Étienne, CNRS, Graduate School Optics Institute, Laboratoire Hubert Curien UMR 5516, Saint-Étienne 42023, France,
Dipartimento di Chimica Industriale, Università degli Studi di Bologna, 40136 Bologna, Italy

Significance Monitoring the real-space motion of the electrons directly involved in ultrafast molecular dynamics is a challenging goal, hindered by the strong contributions of the remaining inactive electrons. Molecular quantum coherences can provide a direct window into elementary electronic dynamics, but they could not be separately imaged so far. Here, we demonstrate a time- and frequency-resolved X-ray diffraction technique, which can employ existing stochastic X-ray pulses to separately image the coherence contributions. The technique can selectively follow the relevant electrons involved in the ultrafast dynamics and identify the confined molecular regions covered by their motion. It enables readily feasible measurements and can be straightforwardly extended to full three-dimensional imaging via X-ray and electron diffraction.

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Research Organization:: Univ. of California, Irvine, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0019484

OSTI ID:: 1785155

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 22 Vol. 118; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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