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

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5116816 · OSTI ID:1577613
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
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Here, 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. Finally, 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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1577613
Alternate ID(s):
OSTI ID: 1656530
Journal Information:
Journal of Chemical Physics, Vol. 151, Issue 12; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

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