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Characterizing the Photochemistry an...

Moss, Olivia Caroline,

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Characterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy /

Record Type:	Electronic resources : Monograph/item
Title/Author:	Characterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy // Olivia Caroline Moss.
Author:	Moss, Olivia Caroline,
Description:	1 electronic resource (87 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 86-12, Section: B.
Contained By:	Dissertations Abstracts International86-12B.
Subject:	Physical chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=31844856
ISBN:	9798286444878

Characterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy /
Moss, Olivia Caroline,

Characterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy /Olivia Caroline Moss. - 1 electronic resource (87 pages)

Source: Dissertations Abstracts International, Volume: 86-12, Section: B.

Marine chromophoric dissolved organic matter (mCDOM) is a large and complex class of material predominantly found at the air-water interface in bodies of water. While it is known to generate radicals and unwanted byproducts, such as HONO· and ·OH, the mechanism of formation for these products currently is unknown. In this dissertation, a bottom-up approach is utilized to investigate possible reaction pathways by scaling down to small-molecule models of mCDOM. Namely, this dissertation investigates the photochemistry and photophysics of benzoylbenzoates (BBA¯). Analysis of the UV spectrum of the deprotonated species reveals two dominant processes upon photoexcitation of 4BBA¯, tag loss and decarboxylation. Analysis of the cold vibrational bands of the UV photoproducts of 2BBA¯ indicate the presence of a isomeric decarboxylate to that of 4BBA¯, as well as a radical carbanion that arises from HOCO∙ loss. This work then is extended to formylbenzoates, FBA¯, to understand isomerization following decarboxylation. FBA¯ is a structurally simpler analog to BBA¯ with similar barriers for isomerization following decarboxylation. This goal is achieved by using a H2 messenger tag as a vibrational reporter for the location of the nascent charge center in the phenide species generated by decarboxylation. Isomer-selective infrared spectra confirm facile migration of the carbanion charge center.

English

ISBN: 9798286444878Subjects--Topical Terms:

1981412
Physical chemistry.
Subjects--Index Terms:

Benzoylbenzoate

Characterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy /
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245 1 0 $a Characterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy / $c Olivia Caroline Moss.
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500 $a Advisors: Johnson, Mark A. Committee members: Vaccaro, Patrick H.; Hazari, Nilay.
502 $b Ph.D. $c Yale University $d 2025.
520 $a Marine chromophoric dissolved organic matter (mCDOM) is a large and complex class of material predominantly found at the air-water interface in bodies of water. While it is known to generate radicals and unwanted byproducts, such as HONO· and ·OH, the mechanism of formation for these products currently is unknown. In this dissertation, a bottom-up approach is utilized to investigate possible reaction pathways by scaling down to small-molecule models of mCDOM. Namely, this dissertation investigates the photochemistry and photophysics of benzoylbenzoates (BBA¯). Analysis of the UV spectrum of the deprotonated species reveals two dominant processes upon photoexcitation of 4BBA¯, tag loss and decarboxylation. Analysis of the cold vibrational bands of the UV photoproducts of 2BBA¯ indicate the presence of a isomeric decarboxylate to that of 4BBA¯, as well as a radical carbanion that arises from HOCO∙ loss. This work then is extended to formylbenzoates, FBA¯, to understand isomerization following decarboxylation. FBA¯ is a structurally simpler analog to BBA¯ with similar barriers for isomerization following decarboxylation. This goal is achieved by using a H2 messenger tag as a vibrational reporter for the location of the nascent charge center in the phenide species generated by decarboxylation. Isomer-selective infrared spectra confirm facile migration of the carbanion charge center.
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590 $a School code: 0265
650 4 $a Physical chemistry. $3 1981412
650 4 $a Atmospheric chemistry. $3 544140
650 4 $a Physics. $3 516296
653 $a Benzoylbenzoate
653 $a Formylbenzoate
653 $a Photochemistry
653 $a Photophysics
653 $a Marine chromophoric dissolved organic matter
690 $a 0494
690 $a 0371
690 $a 0605
710 2 $a Yale University. $b Chemistry. $e degree granting institution. $3 3770408
720 1 $a Johnson, Mark A. $e degree supervisor.
773 0 $t Dissertations Abstracts International $g 86-12B.
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791 $a Ph.D.
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