Sulfur 2p ionization energies of H2S, OCS, SO2, and CS2

We demonstrate site-specific X-ray induced fragmentation across the sulfur L-edge of protonated cystine, the dimer of the amino acid cysteine. Ion yield NEXAFS were performed in the gas phase using electrospray ionization (ESI) in combination with an ion trap. The interpretation of the sulfur L-edge NEXAFS spectrum is supported by Restricted Open-Shell Configuration Interaction (ROCIS) calculations. The fragmentation pathway of triply charged cystine ions was modeled by Molecular Dynamics (MD) simulations. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons. The disulfide bridge breaks for resonant excitation at lower photon energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments initially formed subsequently break into smaller fragments.

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“…This is in reasonable agreement with the ionization energy of other small sulfur-containing molecules, which has a value of 171 eV. 36 …”

Section: Resultssupporting

confidence: 84%

X-ray Induced Fragmentation of Protonated Cystine

et al. 2022

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“…S2p photoelectron spectrum (circles) of a beam of clusters and free monomers of SO 2 produced with a stagnation pressure of 1.97 bar and nozzle temperature of 301 K. The spectrum is decomposed into contributions from clusters (dark colored area) and free monomers (light color) by means of least-squares fitting as detailed in the text. Energy calibration is achieved by assigning the vertical 2p 1=2 ionization energy of the monomer to 175.99(3) eV (Coville and Thomas 1995).…”

Section: Resultsmentioning

confidence: 99%

“…The instrumental broadening based on these experimental settings is approximately Gaussian and with a full-width-at-half-maximum (fwhm) around 90 meV. The binding energy is calibrated to the vertical ionization energies for the S2p 3=2 and S2p 1=2 levels in gaseous SO 2 , which are reported as 174.78 § 0:03 eV and 175.99 § 0:03 eV, respectively (Coville and Thomas 1995).…”

Section: Methodsmentioning

confidence: 99%

Formation and Growth of Clusters of Sulfur Dioxide

Harnes

Abu-samha

Winkler

et al. 2015

Aerosol Science and Technology

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Formation and growth of neutral SO 2 clusters is investigated in an adiabatic-expansion setup by means of sulfur 2p (S2p) photoelectron spectroscopy and theoretical modeling. The shift in S2p ionization energy between the cluster and a single molecule, i.e., IE(cluster)-IE(monomer), is recorded and used to monitor the mean cluster size over a wide range of expansion conditions. The produced clusters were shown to fall into two different size regimes. Comparison between theoretical simulations and experimental observations suggests that while the smallest clusters belong to the ultrafine particle mode and have a liquidlike structure, the larger clusters belong to the accumulation mode of fine particles and possibly have a frozen cluster core. The transition between the two size/structure regimes occurs over a narrow interval in expansion conditions and may possibly reflect a change in growth mechanism from monomer addition to growth by cluster-cluster collisions.

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“…All spectra were collected at the magic angle of 54.7 • , with the electrons entering the analyzer retarded to a pass energy of 10 eV, corresponding to a kinetic-energy resolution of 20 meV. The PES was calibrated by assuming a value of 171.93(3) eV for the ionization energy of the S 2p 1/2 level as published by Coville et al, 22 while the AES was calibrated by using the value of 37.76(3) eV for the double-ionization energy of the 2 1 dicationic state as reported by Eland. 6 This spectral feature could be related to lines in the present AES -independent of the assignment -by comparing the present experimental energy separation of the states assigned to B and 2 3 as well as the splitting of the latter state by 40 meV with the values for the states 2 1 and 2 3 reported by Eland.…”

Section: Methodsmentioning

confidence: 99%

A comprehensive study of the vibrationally resolved S 2p−1 Auger electron spectrum of carbonyl sulfide

Sekushin

Püttner

Fink

et al. 2012

The Journal of Chemical Physics

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High-resolution normal Auger-electron spectra of carbonyl sulfide subsequent to S 2p(-1) photoionization at photon energies of 200, 220, and 240 eV are reported along with corresponding photoelectron spectra. In addition, theoretical results are presented that take the core-hole orientation of the various spin-orbit-split and molecular-field-split S 2p(-1) states into account. Auger transitions to eight metastable dicationic final states are observed and assigned on the basis of the theoretical results. From Franck-Condon analysis, assuming Morse potentials along the normal coordinates for seven of the observed quasi-stable dicationic final states, information on the potential-energy surfaces is derived and compared with theoretical results from the literature.

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Sulfur 2p ionization energies of H2S, OCS, SO2, and CS2

Cited by 25 publications

References 18 publications

X-ray Induced Fragmentation of Protonated Cystine

X-ray Induced Fragmentation of Protonated Cystine

Formation and Growth of Clusters of Sulfur Dioxide

A comprehensive study of the vibrationally resolved S 2p−1 Auger electron spectrum of carbonyl sulfide

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