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Title: Monitoring molecular nonadiabatic dynamics with femtosecond X-ray diffraction

Abstract

Ultrafast time-resolved X-ray scattering, made possible by free-electron laser sources, provides a wealth of information about electronic and nuclear dynamical processes in molecules. The technique provides stroboscopic snapshots of the time-dependent electronic charge density traditionally used in structure determination and reflects the interplay of elastic and inelastic processes, nonadiabatic dynamics, and electronic populations and coherences. The various contributions to ultrafast off-resonant diffraction from populations and coherences of molecules in crystals, in the gas phase, or from single molecules are surveyed for core-resonant and off-resonant diffraction. Single-molecule N scaling and two-molecule N 2 scaling contributions, where N is the number of active molecules, are compared. Simulations are presented for the excited-state nonadiabatic dynamics of the electron harpooning at the avoided crossing in NaF. We show how a class of multiple diffraction signals from a single molecule can reveal charge-density fluctuations through multidimensional correlation functions of the charge density.

Authors:
; ORCiD logo; ; ORCiD logo
Publication Date:
Research Org.:
Univ. of California, Irvine, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1441126
Alternate Identifier(s):
OSTI ID: 1540297
Grant/Contract Number:  
FG02-04ER15571
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 26; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bennett, Kochise, Kowalewski, Markus, Rouxel, Jérémy R., and Mukamel, Shaul. Monitoring molecular nonadiabatic dynamics with femtosecond X-ray diffraction. United States: N. p., 2018. Web. doi:10.1073/pnas.1805335115.
Bennett, Kochise, Kowalewski, Markus, Rouxel, Jérémy R., & Mukamel, Shaul. Monitoring molecular nonadiabatic dynamics with femtosecond X-ray diffraction. United States. doi:10.1073/pnas.1805335115.
Bennett, Kochise, Kowalewski, Markus, Rouxel, Jérémy R., and Mukamel, Shaul. Mon . "Monitoring molecular nonadiabatic dynamics with femtosecond X-ray diffraction". United States. doi:10.1073/pnas.1805335115.
@article{osti_1441126,
title = {Monitoring molecular nonadiabatic dynamics with femtosecond X-ray diffraction},
author = {Bennett, Kochise and Kowalewski, Markus and Rouxel, Jérémy R. and Mukamel, Shaul},
abstractNote = {Ultrafast time-resolved X-ray scattering, made possible by free-electron laser sources, provides a wealth of information about electronic and nuclear dynamical processes in molecules. The technique provides stroboscopic snapshots of the time-dependent electronic charge density traditionally used in structure determination and reflects the interplay of elastic and inelastic processes, nonadiabatic dynamics, and electronic populations and coherences. The various contributions to ultrafast off-resonant diffraction from populations and coherences of molecules in crystals, in the gas phase, or from single molecules are surveyed for core-resonant and off-resonant diffraction. Single-molecule ∝ N scaling and two-molecule ∝ N 2 scaling contributions, where N is the number of active molecules, are compared. Simulations are presented for the excited-state nonadiabatic dynamics of the electron harpooning at the avoided crossing in NaF. We show how a class of multiple diffraction signals from a single molecule can reveal charge-density fluctuations through multidimensional correlation functions of the charge density.},
doi = {10.1073/pnas.1805335115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 26,
volume = 115,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1805335115

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Cited by: 4 works
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