자료유형  

 학위논문

Control Number  

0016931476

International Standard Book Number  

9798379781019

Dewey Decimal Classification Number  

541

Main Entry-Personal Name  

Stropoli, Santino James.

Publication, Distribution, etc. (Imprint  

[S.l.] : Yale University., 2023

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2023

Physical Description  

1 online resource(163 p.)

General Note  

Source: Dissertations Abstracts International, Volume: 85-01, Section: B.

General Note  

Advisor: Johnson, Mark A. .

Dissertation Note  

Thesis (Ph.D.)--Yale University, 2023.

Restrictions on Access Note  

This item must not be sold to any third party vendors.

Summary, Etc.  

요약Sea Spray Aerosols (SSA) generated from ocean-wave breaking constitute one of the largest sources atmospheric particulate matter, and can exhibit enormous diversity in their chemical composition. Heterogenous reactions occurring at the air-water interface of these SSA particles are thought to play a key role in the regulation of gas-phase oxidants and greenhouse gases in the troposphere, and thus have broad implications for global climate. Unfortunately, the underlying chemical physics associated with interfacial reactivity is poorly understood and large uncertainties in the mechanisms, relative product yields, and kinetics of the processes occurring on SSA surfaces remain. In this dissertation, SSA reactivity is characterized at the molecular level by interrogating the products of collisions between the gaseous pollutants dinitrogen pentoxide (N2O5) and hypochlorous acid (HOCl) with charged water cluster model systems. This is accomplished by implementing a new custom-designed dual-ion trap mass spectrometer with additional temperature control and mass-selective capabilities. This instrument is first used to investigate the chemical speciation of N2O5 reactive uptake on I-‧(D2O)n clusters as a function of cluster size and kinetic energy. The instrument is then integrated with infrared and ultraviolet cryogenic ion spectroscopy interfaces to enable structural characterization of the binary interactions between halides (X− = Cl− , Br− , I− ) and HOCl formed by uptake of HOCl on X− ∙(H2O)n clusters. Analysis of the cold vibrational signatures and electronic structures of the resulting X−⋅HOCl ion-molecule complexes reveals key insights into the influences of hydrogen and halogen bonding motifs on HOCl reactivity. Finally, this approach is applied to more complex organic systems by considering the oxidation of methionine (Met) by HOCl to yield methionine sulfoxide (MetO). Collisions of deprotonated methionine water clusters, Met-‧(H2O)n, with HOCl are found to efficiently generate the expected MetO- oxidation product as well as a reaction intermediate identified as the MetO-∙HCl exit-channel complex. Calculated stationary points along the reactive potential energy surface of Met oxidation support a mechanism based on a cyclic S∙∙∙O∙∙∙H motif.

Subject Added Entry-Topical Term  

Physical chemistry.

Subject Added Entry-Topical Term  

Atmospheric chemistry.

Subject Added Entry-Topical Term  

Biomedical engineering.

Index Term-Uncontrolled  

Halogen bond

Index Term-Uncontrolled  

Hypochlorous acid

Index Term-Uncontrolled  

Interfacial reactivity

Index Term-Uncontrolled  

Mass spectrometry

Index Term-Uncontrolled  

Sea spray aerosol

Index Term-Uncontrolled  

Vibrational spectroscopy

Added Entry-Corporate Name  

Yale University Chemistry

Host Item Entry  

Dissertations Abstracts International. 85-01B.

Host Item Entry  

Dissertation Abstract International

Electronic Location and Access  

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Control Number  

joongbu:641969