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Predicting the photoresponse of soot nuclei: Spectroscopic characteristics of aromatic aggregates containing five-membered rings

Krueger, Rachel A. and Blanquart, Guillaume (2020) Predicting the photoresponse of soot nuclei: Spectroscopic characteristics of aromatic aggregates containing five-membered rings. Combustion and Flame, 217 . pp. 85-92. ISSN 0010-2180. https://resolver.caltech.edu/CaltechAUTHORS:20200420-152852324

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Abstract

Establishing the mechanism for soot nucleation will require in situ experimental characterization of the identity and intermolecular interactions of the initial precursors, and electronic spectroscopy methods have the potential to do both. However, the optical response of polycyclic aromatic hydrocarbon (PAH) dimers and complexes differs significantly from that of the constituent monomers, and studies of soot precursor complexes have largely been limited to PAHs containing only six-membered aromatic rings. Hydrocarbons containing unsaturated five-membered rings are also present in high concentration in flames, and the photoresponse of complexes containing five-membered rings has not yet been examined. In this work, we elucidate the spectroscopic properties of small hydrocarbon complexes containing cyclopentadienyl groups or cyclopenta-fused groups, calculating ground- and excited-state binding energies, optimal excited-state geometries, repulsion energies, and fluorescence emission wavelengths. We show that excited-state distortion of cyclopentadienyl groups allows strong binding and low-energy fluorescence emission compared to similar-sized PAHs, and that a cyclopenta-fused group dramatically lowers the absorption and emission energies for acenaphthylene, dominating excited-state noncovalent interactions—findings that could shed light on the complex electronic properties of flames.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1016/j.combustflame.2019.10.028DOIArticle
ORCID:
AuthorORCID
Krueger, Rachel A.0000-0002-5457-2931
Blanquart, Guillaume0000-0002-5074-9728
Additional Information:© 2019 Published by Elsevier Inc. on behalf of The Combustion Institute. Received 14 June 2019, Revised 31 July 2019, Accepted 18 October 2019, Available online 18 April 2020. R. A. K. acknowledges funding from the NSF Division of Graduate Education (DGE-1745301). The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Funders:
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1745301
Subject Keywords:PAH; Soot nucleation; LIF; Particle inception; Cyclopentadiene; Acenaphthylene
Record Number:CaltechAUTHORS:20200420-152852324
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200420-152852324
Official Citation:Rachel A. Krueger, Guillaume Blanquart, Predicting the photoresponse of soot nuclei: Spectroscopic characteristics of aromatic aggregates containing five-membered rings, Combustion and Flame, Volume 217, 2020, Pages 85-92, ISSN 0010-2180, https://doi.org/10.1016/j.combustflame.2019.10.028. (http://www.sciencedirect.com/science/article/pii/S0010218019304857)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:102673
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:20 Apr 2020 23:14
Last Modified:20 Apr 2020 23:14

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