<mods:mods xmlns:mods="http://www.loc.gov/mods/v3" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xsi:schemaLocation="http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-7.xsd"><mods:titleInfo><mods:title>High-Resolution Photoelectron Imaging of Cryogenically-Cooled Anions</mods:title></mods:titleInfo><mods:name type="personal"><mods:namePart>Zhu, Guozhu</mods:namePart><mods:role><mods:roleTerm type="text">creator</mods:roleTerm></mods:role></mods:name><mods:name type="personal"><mods:namePart>Wang, Lai-Sheng</mods:namePart><mods:role><mods:roleTerm type="text">Advisor</mods:roleTerm></mods:role></mods:name><mods:name type="personal"><mods:namePart>Diebold, Gerald</mods:namePart><mods:role><mods:roleTerm type="text">Reader</mods:roleTerm></mods:role></mods:name><mods:name type="personal"><mods:namePart>Rose-Petruck, Christoph</mods:namePart><mods:role><mods:roleTerm type="text">Reader</mods:roleTerm></mods:role></mods:name><mods:name type="corporate"><mods:namePart>Brown University. Department of Chemistry</mods:namePart><mods:role><mods:roleTerm type="text">sponsor</mods:roleTerm></mods:role></mods:name><mods:originInfo><mods:copyrightDate>2019</mods:copyrightDate></mods:originInfo><mods:physicalDescription><mods:extent>xviii, 168 p.</mods:extent><mods:digitalOrigin>born digital</mods:digitalOrigin></mods:physicalDescription><mods:note type="thesis">Thesis (Ph. D.)--Brown University, 2019</mods:note><mods:genre authority="aat">theses</mods:genre><mods:abstract>Photoelectron spectroscopy (PES) is a powerful technique to investigate the electronic structure and chemical bonding of gaseous anions and the corresponding neutrals upon electron detachment. The Wang lab first introduced electrospray ionization (ESI) to spectroscopy by developing a magnetic-bottle PES apparatus with an ESI ion source to study multiply-charged anions. The development of the third-generation ESI-PES apparatus at Brown by coupling a cryogenically-controlled Paul trap with high-resolution PE imaging has enabled accurate vibrational and electronic information to be obtained for singly charged anions produced by ESI and the neutral radicals. Here, the thesis work has focused on both non-resonant and resonant PES of cryogenically-cooled anions. &#13;
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PES is usually done non-resonantly at the fixed laser wavelength. The first research project is to accurately measure the electron affinity (EA) of tetracyanoquinodimethane (TCNQ), an important organic electron acceptor, to be 3.383 ± 0.001 eV, which was erroneously reported in the literatures. High-resolution PES studies on fullerene-related anions, including C59N−, H2O@C60− and H2O@C59N−, have yielded accurate EAs and vibrational structures for the corresponding neutral fullerenes. The weak intramolecular interactions between the encapsulated water molecule and the cage anions in H2O@C60− and H2O@C59N− have also been probed. &#13;
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Anions with dipolar neutral cores can have dipole-bound excited states (DBSs) just below the electron detachment threshold. Optical excitations to vibrational levels of DBS will induce vibrational autodetachment. DBSs of cryogenically-cooled phenoxide and thiophenoxide anions have been observed below the detachment thresholds. Vibrational autodetachments from the DBS levels in the resonant PES result in highly non-Franck-Condon photoelectron spectra, which have shown to be an effective method to obtain vibrational information of dipolar neutral radicals. In addition, DBSs of tautomeric deprotonated cytosine anions have been investigated, yielding tautomer-specific information in the resonant PES. &#13;
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Molecule with vanishing dipole moment but large quadrupole moment can weakly bind an electron to form the quadrupole-bound anion. The first observation of excited quadrupole-bound state in the 4-cyanophenoxide anion, which shows similar autodetachment properties as DBS, will be discussed.</mods:abstract><mods:subject authority="fast" authorityURI="http://id.worldcat.org/fast" valueURI="http://id.worldcat.org/fast/01061561"><mods:topic>Photoelectron spectroscopy</mods:topic></mods:subject><mods:subject><mods:topic>Physical Chemistry</mods:topic></mods:subject><mods:subject authority="fast" authorityURI="http://id.worldcat.org/fast" valueURI="http://id.worldcat.org/fast/00809642"><mods:topic>Anions</mods:topic></mods:subject><mods:language><mods:languageTerm authority="iso639-2b">English</mods:languageTerm></mods:language><mods:recordInfo><mods:recordContentSource authority="marcorg">RPB</mods:recordContentSource><mods:recordCreationDate encoding="iso8601">20190603</mods:recordCreationDate></mods:recordInfo><mods:identifier type="doi">10.26300/cs1z-0a57</mods:identifier><mods:accessCondition type="rights statement" xlink:href="http://rightsstatements.org/vocab/InC/1.0/">In Copyright</mods:accessCondition><mods:accessCondition type="restriction on access">Collection is open for research.</mods:accessCondition><mods:typeOfResource authority="primo">dissertations</mods:typeOfResource></mods:mods>