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Characterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy
Characterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202103023
- ISBN
- 9798286444878
- DDC
- 541
- 서명/저자
- Characterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy
- 발행사항
- [Sl] : Yale University, 2025
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2025
- 형태사항
- 87 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-12, Section: B.
- 주기사항
- Advisor: Johnson, Mark A.
- 학위논문주기
- Thesis (Ph.D.)--Yale University, 2025.
- 초록/해제
- 요약Marine 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.
- 일반주제명
- Physical chemistry
- 일반주제명
- Atmospheric chemistry
- 일반주제명
- Physics
- 키워드
- Benzoylbenzoate
- 키워드
- Formylbenzoate
- 키워드
- Photochemistry
- 키워드
- Photophysics
- 기타저자
- Yale University Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-12B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■006m o d
■007cr#unu||||||||
■020 ▼a9798286444878
■035 ▼a(MiAaPQ)AAI31844856
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a541
■1001 ▼aMoss, Olivia Caroline.
■24510▼aCharacterizing the Photochemistry and Photophysics of Benzoylbenzoate and Formylbenzoate Anions Using Cryogenic Ion Spectroscopy
■260 ▼a[Sl]▼bYale University▼c2025
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2025
■300 ▼a87 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-12, Section: B.
■500 ▼aAdvisor: Johnson, Mark A.
■5021 ▼aThesis (Ph.D.)--Yale University, 2025.
■520 ▼aMarine 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.
■590 ▼aSchool code: 0265.
■650 4▼aPhysical chemistry
■650 4▼aAtmospheric chemistry
■650 4▼aPhysics
■653 ▼aBenzoylbenzoate
■653 ▼aFormylbenzoate
■653 ▼aPhotochemistry
■653 ▼aPhotophysics
■653 ▼aMarine chromophoric dissolved organic matter
■690 ▼a0494
■690 ▼a0371
■690 ▼a0605
■71020▼aYale University▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-12B.
■790 ▼a0265
■791 ▼aPh.D.
■792 ▼a2025
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17356718▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
