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Title: A combined multi-reference pump-probe simulation method with application to XUV signatures of ultrafast methyl iodide photodissociation

Abstract

UV pump-XUV/X-ray probe measurements have been successfully applied in the study of photo-induced chemical reactions. Although rich element-specific electronic structure information is accessible within XUV/X-ray (inner-shell) absorption spectra, it can be difficult to interpret the chemistry directly from the spectrum without supporting theoretical simulations. A multireference method to completely simulate UV pump-XUV/X-ray probe measurement has been developed and applied to study the methyl iodide photodissociation process. Multireference, fewest-switches surface hopping (FSSH) trajectories were used to explore the coupled electronic and ionic dynamics upon photoexcitation of methyl iodide. Interpretation of previous measurements is provided by associated multireference, restricted active space, inner-shell spectral simulations. This combination of multireference FSSH trajectories and XUV spectra provides an interpretation of transient features appearing in previous measurements within the first 100 fs after photoexcitation and validates the significant branching ratio in the final excited-state population. This methodology should prove useful for interpretation of the increasing number of inner-shell probe studies of molecular excited states or for directing new experiments toward interesting regions of the potential energy landscape.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Stockholm Univ. (Sweden). AlbaNova University Center
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Molecular Foundry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)
OSTI Identifier:
1577613
Alternate Identifier(s):
OSTI ID: 1656530
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 12; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Wang, Han, Odelius, Michael, and Prendergast, David. A combined multi-reference pump-probe simulation method with application to XUV signatures of ultrafast methyl iodide photodissociation. United States: N. p., 2019. Web. https://doi.org/10.1063/1.5116816.
Wang, Han, Odelius, Michael, & Prendergast, David. A combined multi-reference pump-probe simulation method with application to XUV signatures of ultrafast methyl iodide photodissociation. United States. https://doi.org/10.1063/1.5116816
Wang, Han, Odelius, Michael, and Prendergast, David. Wed . "A combined multi-reference pump-probe simulation method with application to XUV signatures of ultrafast methyl iodide photodissociation". United States. https://doi.org/10.1063/1.5116816. https://www.osti.gov/servlets/purl/1577613.
@article{osti_1577613,
title = {A combined multi-reference pump-probe simulation method with application to XUV signatures of ultrafast methyl iodide photodissociation},
author = {Wang, Han and Odelius, Michael and Prendergast, David},
abstractNote = {UV pump-XUV/X-ray probe measurements have been successfully applied in the study of photo-induced chemical reactions. Although rich element-specific electronic structure information is accessible within XUV/X-ray (inner-shell) absorption spectra, it can be difficult to interpret the chemistry directly from the spectrum without supporting theoretical simulations. A multireference method to completely simulate UV pump-XUV/X-ray probe measurement has been developed and applied to study the methyl iodide photodissociation process. Multireference, fewest-switches surface hopping (FSSH) trajectories were used to explore the coupled electronic and ionic dynamics upon photoexcitation of methyl iodide. Interpretation of previous measurements is provided by associated multireference, restricted active space, inner-shell spectral simulations. This combination of multireference FSSH trajectories and XUV spectra provides an interpretation of transient features appearing in previous measurements within the first 100 fs after photoexcitation and validates the significant branching ratio in the final excited-state population. This methodology should prove useful for interpretation of the increasing number of inner-shell probe studies of molecular excited states or for directing new experiments toward interesting regions of the potential energy landscape.},
doi = {10.1063/1.5116816},
journal = {Journal of Chemical Physics},
number = 12,
volume = 151,
place = {United States},
year = {2019},
month = {9}
}

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