Specific production of very long-lived core-excited sulfur atoms by 2p⁻¹σ* excitation of the OCS molecule followed by ultrafast dissociation

Abstract

A core-excited sulfur state with a lifetime almost one order of magnitude longer than in molecular 2p core-hole states is selectively produced by ultrafast dissociation of S 2p → σ* excited OCS. Clear evidence for this is provided by strong atomic peaks (20% of the total intensity) in x-ray fluorescence but very weak ones (2%) in the corresponding resonant Auger spectrum. Corroborating the assignment of the spectra, ab initio calculations explain the enhanced lifetime: the Auger decay of the produced 3D3 (2p53p5) sulfur state is strongly decreased as it contradicts a newly derived propensity rule of the L2,3MM Auger decay.

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

“…Complementary calculations of the AES had been reported by Carroll et al 12 and by Minelli et al 15 On the other hand, several studies exist of resonant AES (Ref. [16][17][18] as well as of resonant X-ray fluorescence spectra of this molecule. [18][19][20] In this context, a core-excited state of the sulphur atom with an exceptionally long core-hole lifetime had been observed.…”

“…Auger transition rates were determined as in Ref. 36 using the Auger transition integrals of Chen et al 39 and the known spin-orbit splitting parameters 18,40 of this molecule. The results for final states relevant to this work are collected in Table I, while the data for the complete set of the calculated final states is available in the supplementary material of this article.…”

“…[18][19][20] In this context, a core-excited state of the sulphur atom with an exceptionally long core-hole lifetime had been observed. 18,19 In the present work, we present a high-resolution AES that exhibits vibrational structures for eight transitions. These fine structures are assigned to C−O or C−S stretching vibrational modes, and a Franck-Condon analysis allows to derive detailed information on the potential-energy surfaces.…”

“…[16][17][18] as well as of resonant X-ray fluorescence spectra of this molecule. [18][19][20] In this context, a core-excited state of the sulphur atom with an exceptionally long core-hole lifetime had been observed. 18,19 In the present work, we present a high-resolution AES that exhibits vibrational structures for eight transitions.…”

Angular and dynamical properties in resonant inelastic x-ray scattering: Case study of chlorine-containing molecules

“…With such techniques, a wealth of information can be obtained on ultrafast nuclear motion [1][2][3][4][5][6], ultrafast dissociation processes [7][8][9][10][11][12][13][14][15], interference phenomena [14], etc. The competing process, i.e., radiative decay, has been less investigated for several reasons.…”