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Title: Near and Above Ionization Electronic Excitations with Non-Hermitian Real-Time Time-Dependent Density Functional Theory

We present a real-time time-dependent density functional theory (RT-TDDFT) prescription for capturing near and post-ionization excitations based on non-Hermitian von Neumann density matrix propagation with atom-centered basis sets, tuned range-separated DFT, and a phenomenological imaginary molecular orbital-based absorbing potential to mimic coupling to the continuum. The computed extreme ultraviolet absorption spectra for acetylene (C2H2), water (H2O), and Freon 12 (CF2Cl2) agree well with electron energy loss spectroscopy (EELS) data over the range 0 to 50 eV. The absorbing potential removes spurious high energy finite basis artifacts, yielding correct bound to bound transitions, metastable (autoionizing) resonance states, and consistent overall absorption shapes.
Authors:
;
Publication Date:
OSTI Identifier:
1114891
Report Number(s):
PNNL-SA-97859
47703; KC0301020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Theory and Computation, 9(11):4939-4946
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
Density Functional Theory; electronic; excitations; ultraviolet; absorption; Non-Hermitian; Environmental Molecular Sciences Laboratory