Oscar Paredes Mellone

All Publications

• Investigating the electronic structure of high explosives with X-ray Raman spectroscopy. Scientific reports Paredes-Mellone, O. A., Nielsen, M. H., Vinson, J., Moua, K., Skoien, K. D., Sokaras, D., Willey, T. M. 2022; 12 (1): 19460

  Abstract

  We investigate the sensitivity and potential of a synergistic experiment-theory X-ray Raman spectroscopy (XRS) methodology on revealing and following the static and dynamic electronic structure of high explosive molecular materials. We show that advanced ab-initio theoretical calculations accounting for the core-hole effect based on the Bethe-Salpeter Equation (BSE) approximation are critical for accurately predicting the shape and the energy position of the spectral features of C and N core-level spectra. Moreover, the incident X-ray dose typical XRS experiments require can induce, in certain unstable structures, a prominent radiation damage at room temperature. Upon developing a compatible cryostat module for enabling cryogenic temperatures ([Formula: see text] 10 K) we suppress the radiation damage and enable the acquisition of reliable experimental spectra in excellent agreement with the theory. Overall, we demonstrate the high sensitivity of the recently available state-of-the-art X-ray Raman spectroscopy capabilities in characterizing the electronic structure of high explosives. At the same time, the high accuracy of the theoretical approach may enable reliable identification of intermediate structures upon rapid chemical decomposition during detonation. Considering the increasing availability of X-ray free-electron lasers, such a combined experiment-theory approach paves the way for time-resolved dynamic studies of high explosives under detonation conditions.

  View details for DOI 10.1038/s41598-022-24066-z

  View details for PubMedID 36376464

• Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS2. ACS nano Garcia-Esparza, A. T., Park, S., Abroshan, H., Paredes Mellone, O. A., Vinson, J., Abraham, B., Kim, T. R., Nordlund, D., Gallo, A., Alonso-Mori, R., Zheng, X., Sokaras, D. 2022

  Abstract

  The nature of the S-vacancy is central to controlling the electronic properties of monolayer MoS2. Understanding the geometric and electronic structures of the S-vacancy on the basal plane of monolayer MoS2 remains elusive. Here, operando S K-edge X-ray absorption spectroscopy shows the formation of clustered S-vacancies on the basal plane of monolayer MoS2 under reaction conditions (H2 atmosphere, 100-600 °C). First-principles calculations predict spectral fingerprints consistent with the experimental results. The Mo K-edge extended X-ray absorption fine structure shows the local structure as coordinatively unsaturated Mo with 4.1 ± 0.4 S atoms as nearest neighbors (above 400 °C in an H2 atmosphere). Conversely, the 6-fold Mo-Mo coordination in the crystal remains unchanged. Electrochemistry confirms similar active sites for hydrogen evolution. The identity of the S-vacancy defect on the basal plane of monolayer MoS2 is herein elucidated for applications in optoelectronics and catalysis.

  View details for DOI 10.1021/acsnano.2c01388

  View details for PubMedID 35380038