Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

Structural Dynamics
Benjamin E Van KuikenMunira Khalil

Abstract

Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400 nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps) and decays within 6 ns. The second transient species forms on a timescale of ∼400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowest-lying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.

References

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Jun 21, 2012·The Journal of Physical Chemistry Letters·Benjamin E Van KuikenMunira Khalil

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Citations

Nov 20, 2018·Chemistry : a European Journal·Sebastian EckertAlexander Föhlisch
Apr 2, 2019·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Philippe Wernet
Feb 13, 2018·Physical Chemistry Chemical Physics : PCCP·Maria NaumovaMichael Rübhausen
Jun 28, 2019·The Journal of Physical Chemistry. B·Jesper NorellMichael Odelius
Oct 31, 2017·Journal of the American Chemical Society·Aditi BhattacherjeeStephen R Leone
Dec 17, 2021·The Journal of Physical Chemistry Letters·Yujin KimTae Kyu Kim

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Methods Mentioned

BETA
X-ray
Fluorescence

Software Mentioned

ORCA

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