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Title: X-ray linear and non-linear spectroscopy of the ESCA molecule

Abstract

Linear and nonlinear X-ray spectroscopy hold the promise to provide a complementary tool to the available ample body of terahertz to UV spectroscopic techniques, disclosing information about the electronic structure and the dynamics of a large variety of systems, spanning from transition metals to organic molecules. While experimental free electron laser facilities continue to develop, theory may take the lead in modeling and inspiring new cutting edge experiments, paving the way to their future use. As an example, the not-yet-available two-dimensional coherent X-ray spectroscopy (2DCXS), conceptually similar to 2D-NMR, is expected to provide a wealth of information about molecular structure and dynamics with an unprecedented level of detail. In the present contribution, we focus on the simulation of linear and non-linear (2DCXS) spectra of the ESCA molecule. The molecule has four inequivalent carbon K-edges and has been widely used as a benchmark for photoelectron spectroscopy. Two theoretical approaches for the computation of the system manifold of states, namely, TDDFT and RASSCF/RASPT2, are compared, and the possible signals that may appear in a 2DCXS experiment and their origin are surveyed.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. degli Studi di Bologna (Italy)
  2. Univ. of California, Irvine, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Irvine, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1613248
Grant/Contract Number:  
SC0019484
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 11; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; Chemistry; Physics; Feynman diagrams; Transition moment; Spectroscopy; Four wave mixing; Band gap; Gas phase; Restricted active-space self-consistent field method; Atomic spectral lines; Free electron lasers

Citation Formats

Nenov, Artur, Segatta, Francesco, Bruner, Adam, Mukamel, Shaul, and Garavelli, Marco. X-ray linear and non-linear spectroscopy of the ESCA molecule. United States: N. p., 2019. Web. https://doi.org/10.1063/1.5116699.
Nenov, Artur, Segatta, Francesco, Bruner, Adam, Mukamel, Shaul, & Garavelli, Marco. X-ray linear and non-linear spectroscopy of the ESCA molecule. United States. https://doi.org/10.1063/1.5116699
Nenov, Artur, Segatta, Francesco, Bruner, Adam, Mukamel, Shaul, and Garavelli, Marco. Wed . "X-ray linear and non-linear spectroscopy of the ESCA molecule". United States. https://doi.org/10.1063/1.5116699. https://www.osti.gov/servlets/purl/1613248.
@article{osti_1613248,
title = {X-ray linear and non-linear spectroscopy of the ESCA molecule},
author = {Nenov, Artur and Segatta, Francesco and Bruner, Adam and Mukamel, Shaul and Garavelli, Marco},
abstractNote = {Linear and nonlinear X-ray spectroscopy hold the promise to provide a complementary tool to the available ample body of terahertz to UV spectroscopic techniques, disclosing information about the electronic structure and the dynamics of a large variety of systems, spanning from transition metals to organic molecules. While experimental free electron laser facilities continue to develop, theory may take the lead in modeling and inspiring new cutting edge experiments, paving the way to their future use. As an example, the not-yet-available two-dimensional coherent X-ray spectroscopy (2DCXS), conceptually similar to 2D-NMR, is expected to provide a wealth of information about molecular structure and dynamics with an unprecedented level of detail. In the present contribution, we focus on the simulation of linear and non-linear (2DCXS) spectra of the ESCA molecule. The molecule has four inequivalent carbon K-edges and has been widely used as a benchmark for photoelectron spectroscopy. Two theoretical approaches for the computation of the system manifold of states, namely, TDDFT and RASSCF/RASPT2, are compared, and the possible signals that may appear in a 2DCXS experiment and their origin are surveyed.},
doi = {10.1063/1.5116699},
journal = {Journal of Chemical Physics},
number = 11,
volume = 151,
place = {United States},
year = {2019},
month = {9}
}

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