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:
-
[1];
[2]
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- 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). Chemical Sciences, Geosciences, and 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. https://doi.org/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. https://doi.org/10.1098/rsta.2017.0473. https://www.osti.gov/servlets/purl/1528863.
@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 = {Mon Apr 01 00:00:00 EDT 2019},
month = {Mon Apr 01 00:00:00 EDT 2019}
}
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