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Title: Two-photon absorption in conjugated energetic molecule

Abstract

Time-dependent density functional theory (TD-DFT) is used to investigate the relationship between molecular structure and one- and two-photon absorption (OPA and TPA, respectively) properties in novel and recently synthesized conjugated energetic molecules (CEMs). The molecular structure of CEMs can be strategically altered to influence the heat of formation and oxygen balance, two factors that can contribute to the sensitivity and strength of an explosive material. OPA and TPA are sensitive to changes in molecular structure as well, influencing optical range of excitation. We find calculated vertical excitation energies in good agreement with experiment for most molecules. Peak TPA intensities are significant and on the order of 102 GM. Natural transition orbitals for essential electronic states defining TPA peaks of relatively large intensity to examine the character of relevant transitions. Minor modification of molecular substituents, such as additional oxygen and other functional groups, produces significant changes in electronic structure, OPA, TPA, and improves the oxygen balance. Results show that select molecules are apt to nonlinear absorption, opening the possibility for controlled, direct optical initiation of CEMs through photochemical pathways.

Authors:
 [1];  [2];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Univ. of Southern California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1338766
Report Number(s):
LA-UR-16-20834
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 26; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry

Citation Formats

Bjorgaard, Josiah August, Sifain, Andrew, Nelson, Tammie Renee, Myers, Thomas Winfield, Veauthier, Jacqueline Marie, Chavez, David E., Scharff, Robert Jason, and Tretiak, Sergei. Two-photon absorption in conjugated energetic molecule. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b03136.
Bjorgaard, Josiah August, Sifain, Andrew, Nelson, Tammie Renee, Myers, Thomas Winfield, Veauthier, Jacqueline Marie, Chavez, David E., Scharff, Robert Jason, & Tretiak, Sergei. Two-photon absorption in conjugated energetic molecule. United States. doi:10.1021/acs.jpca.6b03136.
Bjorgaard, Josiah August, Sifain, Andrew, Nelson, Tammie Renee, Myers, Thomas Winfield, Veauthier, Jacqueline Marie, Chavez, David E., Scharff, Robert Jason, and Tretiak, Sergei. Fri . "Two-photon absorption in conjugated energetic molecule". United States. doi:10.1021/acs.jpca.6b03136. https://www.osti.gov/servlets/purl/1338766.
@article{osti_1338766,
title = {Two-photon absorption in conjugated energetic molecule},
author = {Bjorgaard, Josiah August and Sifain, Andrew and Nelson, Tammie Renee and Myers, Thomas Winfield and Veauthier, Jacqueline Marie and Chavez, David E. and Scharff, Robert Jason and Tretiak, Sergei},
abstractNote = {Time-dependent density functional theory (TD-DFT) is used to investigate the relationship between molecular structure and one- and two-photon absorption (OPA and TPA, respectively) properties in novel and recently synthesized conjugated energetic molecules (CEMs). The molecular structure of CEMs can be strategically altered to influence the heat of formation and oxygen balance, two factors that can contribute to the sensitivity and strength of an explosive material. OPA and TPA are sensitive to changes in molecular structure as well, influencing optical range of excitation. We find calculated vertical excitation energies in good agreement with experiment for most molecules. Peak TPA intensities are significant and on the order of 102 GM. Natural transition orbitals for essential electronic states defining TPA peaks of relatively large intensity to examine the character of relevant transitions. Minor modification of molecular substituents, such as additional oxygen and other functional groups, produces significant changes in electronic structure, OPA, TPA, and improves the oxygen balance. Results show that select molecules are apt to nonlinear absorption, opening the possibility for controlled, direct optical initiation of CEMs through photochemical pathways.},
doi = {10.1021/acs.jpca.6b03136},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 26,
volume = 120,
place = {United States},
year = {2016},
month = {6}
}

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Cited by: 4 works
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Works referencing / citing this record:

Azido and Tetrazolo 1,2,4,5-Tetrazine N-Oxides
journal, February 2017

  • Chavez, David E.; Parrish, Damon A.; Mitchell, Lauren
  • Angewandte Chemie International Edition, Vol. 56, Issue 13
  • DOI: 10.1002/anie.201612496

Azido and Tetrazolo 1,2,4,5-Tetrazine N-Oxides
journal, February 2017

  • Chavez, David E.; Parrish, Damon A.; Mitchell, Lauren
  • Angewandte Chemie International Edition, Vol. 56, Issue 13
  • DOI: 10.1002/anie.201612496