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Title: Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation

Abstract

The coherence and dephasing of vibrational motions of molecules constitute an integral part of chemical dynamics, influence material properties and underpin schemes to control chemical reactions. Considerable progress has been made in understand- ing vibrational coherence through spectroscopic measurements, but precise, direct measurement of the structure of a vibrating excited-state polyatomic organic molecule has remained unworkable. Here, we measure the time-evolving molecular structure of optically excited N-methylmorpholine through scattering with ultrashort X-ray pulses. The scattering signals are corrected for the differences in electron density in the excited electronic state of the molecule in comparison to the ground state. The experiment maps the evolution of the molecular geometry with femtosecond resolution, showing coherent motion that survives electronic relaxation and seems to persist for longer than previously seen using other methods.

Authors:
 [1]; ORCiD logo [1];  [2];  [1];  [2];  [3];  [3];  [3];  [3];  [3];  [1];  [1];  [1];  [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Brown Univ., Providence, RI (United States)
  2. Univ. of Edinburgh, Edinburgh (United Kingdom)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Brown Univ., Providence, RI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Contributing Org.:
SLAC National Laboratory; University of Edinburgh
OSTI Identifier:
1526046
Alternate Identifier(s):
OSTI ID: 1596774
Grant/Contract Number:  
AC02-76SF00515; SC0017995
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 11; Journal Issue: 8; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Stankus, Brian, Yong, Haiwang, Zotev, Nikola, Ruddock, Jennifer M., Bellshaw, Darren, Lane, Thomas J., Liang, Mengning, Boutet, Sébastien, Carbajo, Sergio, Robinson, Joseph S., Du, Wenpeng, Goff, Nathan, Chang, Yu, Koglin, Jason E., Minitti, Michael P., Kirrander, Adam, and Weber, Peter M.. Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation. United States: N. p., 2019. Web. https://doi.org/10.1038/s41557-019-0291-0.
Stankus, Brian, Yong, Haiwang, Zotev, Nikola, Ruddock, Jennifer M., Bellshaw, Darren, Lane, Thomas J., Liang, Mengning, Boutet, Sébastien, Carbajo, Sergio, Robinson, Joseph S., Du, Wenpeng, Goff, Nathan, Chang, Yu, Koglin, Jason E., Minitti, Michael P., Kirrander, Adam, & Weber, Peter M.. Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation. United States. https://doi.org/10.1038/s41557-019-0291-0
Stankus, Brian, Yong, Haiwang, Zotev, Nikola, Ruddock, Jennifer M., Bellshaw, Darren, Lane, Thomas J., Liang, Mengning, Boutet, Sébastien, Carbajo, Sergio, Robinson, Joseph S., Du, Wenpeng, Goff, Nathan, Chang, Yu, Koglin, Jason E., Minitti, Michael P., Kirrander, Adam, and Weber, Peter M.. Mon . "Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation". United States. https://doi.org/10.1038/s41557-019-0291-0. https://www.osti.gov/servlets/purl/1526046.
@article{osti_1526046,
title = {Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation},
author = {Stankus, Brian and Yong, Haiwang and Zotev, Nikola and Ruddock, Jennifer M. and Bellshaw, Darren and Lane, Thomas J. and Liang, Mengning and Boutet, Sébastien and Carbajo, Sergio and Robinson, Joseph S. and Du, Wenpeng and Goff, Nathan and Chang, Yu and Koglin, Jason E. and Minitti, Michael P. and Kirrander, Adam and Weber, Peter M.},
abstractNote = {The coherence and dephasing of vibrational motions of molecules constitute an integral part of chemical dynamics, influence material properties and underpin schemes to control chemical reactions. Considerable progress has been made in understand- ing vibrational coherence through spectroscopic measurements, but precise, direct measurement of the structure of a vibrating excited-state polyatomic organic molecule has remained unworkable. Here, we measure the time-evolving molecular structure of optically excited N-methylmorpholine through scattering with ultrashort X-ray pulses. The scattering signals are corrected for the differences in electron density in the excited electronic state of the molecule in comparison to the ground state. The experiment maps the evolution of the molecular geometry with femtosecond resolution, showing coherent motion that survives electronic relaxation and seems to persist for longer than previously seen using other methods.},
doi = {10.1038/s41557-019-0291-0},
journal = {Nature Chemistry},
number = 8,
volume = 11,
place = {United States},
year = {2019},
month = {7}
}

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