Visualizing conical intersection passages via vibronic coherence maps generated by stimulated ultrafast X-ray Raman signals

Keefer, Daniel; Schnappinger, Thomas; de Vivie-Riedle, Regina; Mukamel, Shaul

doi:10.1073/pnas.2015988117

Visualizing conical intersection passages via vibronic coherence maps generated by stimulated ultrafast X-ray Raman signals

Journal Article · Mon Sep 14 00:00:00 EDT 2020 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2015988117· OSTI ID:1660474

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Department of Chemistry, University of California, Irvine, CA 92697-2025,, Department of Physics and Astronomy, University of California, Irvine, CA 92697-2025,
Department of Physics and Astronomy, University of California, Irvine, CA 92697-2025,

Significance

The capabilities of modern X-ray sources have substantially increased the temporal and spectral resolutions for the observation of elementary molecular events. Theoretically, it has been shown that these unique features can be exploited to probe vibronic coherences that emerge when molecules pass through conical intersections. Here, we demonstrate this technique for the photorelaxation of the RNA-nucleobase uracil after UV excitation. The generated coherence maps reveal the path of the nuclear wavepacket on the excited-state surface in the vicinity of the conical intersection. This information is directly accessible from the spectroscopically recorded signal. Being transferrable to other molecules, these coherence maps will provide detailed visualizations of other nonadiabatic passages in the future.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-04ER15571

OSTI ID:: 1660474

Alternate ID(s):: OSTI ID: 1800160

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: 39 Vol. 117; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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