In this paper, we report X-ray absorption and core-level electron spectra of the nucleobase derivative 2-thiouracil at the sulfur L- and L-edges. We used soft X-rays from the free-electron laser FLASH2 for the excitation of isolated molecules and dispersed the outgoing electrons with a magnetic bottle spectrometer. We identified photoelectrons from the 2p core orbital, accompanied by an electron correlation satellite, as well as resonant and non-resonant Coster-Kronig and Auger-Meitner emission at the L- and L-edges, respectively. We used the electron yield to construct X-ray absorption spectra at the two edges. The experimental data obtained are put in the context of the literature currently available on sulfur core-level and 2-thiouracil spectroscopy.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8586990 | PMC |
http://dx.doi.org/10.3390/molecules26216469 | DOI Listing |
Int J Mol Sci
November 2024
Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland.
J Chem Phys
October 2024
Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany.
We present a comprehensive, combined experimental and theoretical study of the core-level photoelectron and near-edge x-ray absorption fine structure (NEXAFS) spectra of 2-thiouracil, 4-thiouracil, and 2,4-dithiouracil at the oxygen 1s, nitrogen 1s, carbon 1s, and the sulfur 2s and 2p edges. X-ray photoelectron spectra were calculated using equation-of-motion coupled-cluster theory (EOM-CCSD), and NEXAFS spectra were calculated using algebraic diagrammatic construction and EOM-CCSD. For the main peaks at O and N 1s as well as the S 2s edge, we find a single photoline.
View Article and Find Full Text PDFPhotochem Photobiol
January 2024
Deutsches Elektronen-Synchrotron DESY, Hamburg, Germany.
The photoinduced relaxation dynamics of nucleobases and their thionated analogs have been investigated extensively over the past decades motivated by their crucial role in organisms and their application in medical and biochemical research and treatment. Most of these studies focused on the spectroscopy of valence electrons and fragmentation. The advent of ultrashort x-ray laser sources such as free-electron lasers, however, opens new opportunities for studying the ultrafast molecular relaxation dynamics utilizing the site- and element-selectivity of x-rays.
View Article and Find Full Text PDFJ Phys Chem A
November 2022
Department of Physics and Astronomy, University of Georgia, Athens, Georgia 30602, United States.
The ultrafast internal conversion and intersystem crossing dynamics of 2-thiouracil (2TU) and 2-thiothymine (2TT) are studied using time-resolved photoelectron spectroscopy to investigate the effect of methylation on the deactivation mechanism. Like other thiobases, the triplet manifold is populated with high quantum yields via the lowest singlet excited state, which is dark in absorption. This study focuses on the lowest triplet state and the role of two minima, with sulfur-out-of-plane and slightly boat-like geometries, in the intersystem crossing dynamics back to the ground state.
View Article and Find Full Text PDFNat Commun
January 2022
Institut für Physik und Astronomie, Universität Potsdam, 14476, Potsdam, Germany.
The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!