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Title: Understanding the effect of thionation on naphthalene diimide using first-principles predictions of near-edge x-ray absorption fine structure spectra

Abstract

The near edge X-ray absorption fine structure (NEXAFS) spectra of naphthalene diimide molecules with increasing degrees of thionation show distinct and systematic changes in the C 1s → π* manifold. However, interpretation of such spectra is difficult using experimental data alone, due to the limitation in experimental NEXAFS resolution. In this work, we have calculated the NEXAFS spectra of naphthalene diimide molecules with increasing degrees of thionation using the density functional theory-based eXcited electron and Core Hole approach. Furthermore, we find that the systematic broadening and intensity reduction in the peaks observed in the π* manifold with increasing thionation are the result of distinct changes in the chemical environment of the outer carbon atoms that are bonded directly to either oxygen or sulfur. Specifically, the C 1s → lowest unoccupied molecular orbital (LUMO) transition energy dramatically decreases with thionation, as the valence electron density of these carbon atoms is increased when highly electronegative oxygen atoms are replaced by less-oxidizing sulfur atoms. It is also shown that significant core level shifts present in naphthalene diimide-based molecule result in a mixing of the LUMO and LUMO + 1 character in the C 1s → π* manifold, meaning that experimentally observed peaks cannotmore » be uniquely associated with the transitions of LUMO, LUMO + 1, etc.« less

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Monash Univ., Clayton, VIC (Australia)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1530413
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 10; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Rundel, Kira, Liang, Yufeng, Welford, Adam, Prendergast, David, and McNeill, Christopher R. Understanding the effect of thionation on naphthalene diimide using first-principles predictions of near-edge x-ray absorption fine structure spectra. United States: N. p., 2019. Web. doi:10.1063/1.5084754.
Rundel, Kira, Liang, Yufeng, Welford, Adam, Prendergast, David, & McNeill, Christopher R. Understanding the effect of thionation on naphthalene diimide using first-principles predictions of near-edge x-ray absorption fine structure spectra. United States. doi:10.1063/1.5084754.
Rundel, Kira, Liang, Yufeng, Welford, Adam, Prendergast, David, and McNeill, Christopher R. Mon . "Understanding the effect of thionation on naphthalene diimide using first-principles predictions of near-edge x-ray absorption fine structure spectra". United States. doi:10.1063/1.5084754. https://www.osti.gov/servlets/purl/1530413.
@article{osti_1530413,
title = {Understanding the effect of thionation on naphthalene diimide using first-principles predictions of near-edge x-ray absorption fine structure spectra},
author = {Rundel, Kira and Liang, Yufeng and Welford, Adam and Prendergast, David and McNeill, Christopher R.},
abstractNote = {The near edge X-ray absorption fine structure (NEXAFS) spectra of naphthalene diimide molecules with increasing degrees of thionation show distinct and systematic changes in the C 1s → π* manifold. However, interpretation of such spectra is difficult using experimental data alone, due to the limitation in experimental NEXAFS resolution. In this work, we have calculated the NEXAFS spectra of naphthalene diimide molecules with increasing degrees of thionation using the density functional theory-based eXcited electron and Core Hole approach. Furthermore, we find that the systematic broadening and intensity reduction in the peaks observed in the π* manifold with increasing thionation are the result of distinct changes in the chemical environment of the outer carbon atoms that are bonded directly to either oxygen or sulfur. Specifically, the C 1s → lowest unoccupied molecular orbital (LUMO) transition energy dramatically decreases with thionation, as the valence electron density of these carbon atoms is increased when highly electronegative oxygen atoms are replaced by less-oxidizing sulfur atoms. It is also shown that significant core level shifts present in naphthalene diimide-based molecule result in a mixing of the LUMO and LUMO + 1 character in the C 1s → π* manifold, meaning that experimentally observed peaks cannot be uniquely associated with the transitions of LUMO, LUMO + 1, etc.},
doi = {10.1063/1.5084754},
journal = {Journal of Chemical Physics},
number = 10,
volume = 150,
place = {United States},
year = {2019},
month = {3}
}

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