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Title: Photochemical pathways in nucleobases measured with an X-ray FEL

Abstract

The conversion of light energy into other molecular energetic degrees of freedom is often dominated by ultrafast, non-adiabatic processes. Femtosecond spectroscopy with optical pulses has helped in shaping our understanding of crucial processes in molecular energy-conversion. The advent of new, ultrashort and bright X-ray free electron laser sources opens the possibility to use X-ray-typical element and site sensitivity for ultrafast molecular research. We introduce two types of spectroscopy, ultrafast Auger and ultrafast X-ray absorption spectroscopy, and discuss their sensitivity to molecular processes. While Auger spectroscopy is able to monitor bond distance changes in the vicinity of an X-ray created core hole, near-edge absorption spectroscopy can deliver high-fidelity information on non-adiabatic transitions involving lone-pair orbitals. We display these features on the example of the UV-excited nucleobase thymine, investigated at the oxygen K-edge. We find a C–O bond elongation in the Auger data in addition to ππ*/nπ* non-adiabatic transition in X-ray near-edge absorption. We compare the results from both methods and draw a conclusive scenario of non-adiabatic molecular relaxation after UV excitation. This article is part of the theme issue ‘Measurement of ultrafast electronic and structural dynamics with X-rays’.

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Potsdam (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1528863
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Philosophical Transactions of the Royal Society. A, Mathematical, Physical and Engineering Sciences
Additional Journal Information:
Journal Volume: 377; Journal Issue: 2145; Journal ID: ISSN 1364-503X
Publisher:
The Royal Society Publishing
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nucleobase; time-resolved X-ray probing; Auger decay; femtosecond laser spectroscopy

Citation Formats

Wolf, Thomas J. A., and Gühr, Markus. Photochemical pathways in nucleobases measured with an X-ray FEL. United States: N. p., 2019. Web. doi:10.1098/rsta.2017.0473.
Wolf, Thomas J. A., & Gühr, Markus. Photochemical pathways in nucleobases measured with an X-ray FEL. United States. doi:10.1098/rsta.2017.0473.
Wolf, Thomas J. A., and Gühr, Markus. Mon . "Photochemical pathways in nucleobases measured with an X-ray FEL". United States. doi:10.1098/rsta.2017.0473.
@article{osti_1528863,
title = {Photochemical pathways in nucleobases measured with an X-ray FEL},
author = {Wolf, Thomas J. A. and Gühr, Markus},
abstractNote = {The conversion of light energy into other molecular energetic degrees of freedom is often dominated by ultrafast, non-adiabatic processes. Femtosecond spectroscopy with optical pulses has helped in shaping our understanding of crucial processes in molecular energy-conversion. The advent of new, ultrashort and bright X-ray free electron laser sources opens the possibility to use X-ray-typical element and site sensitivity for ultrafast molecular research. We introduce two types of spectroscopy, ultrafast Auger and ultrafast X-ray absorption spectroscopy, and discuss their sensitivity to molecular processes. While Auger spectroscopy is able to monitor bond distance changes in the vicinity of an X-ray created core hole, near-edge absorption spectroscopy can deliver high-fidelity information on non-adiabatic transitions involving lone-pair orbitals. We display these features on the example of the UV-excited nucleobase thymine, investigated at the oxygen K-edge. We find a C–O bond elongation in the Auger data in addition to ππ*/nπ* non-adiabatic transition in X-ray near-edge absorption. We compare the results from both methods and draw a conclusive scenario of non-adiabatic molecular relaxation after UV excitation. This article is part of the theme issue ‘Measurement of ultrafast electronic and structural dynamics with X-rays’.},
doi = {10.1098/rsta.2017.0473},
journal = {Philosophical Transactions of the Royal Society. A, Mathematical, Physical and Engineering Sciences},
number = 2145,
volume = 377,
place = {United States},
year = {2019},
month = {4}
}

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