語系:
繁體中文
English
說明(常見問題)
回圖書館首頁
手機版館藏查詢
登入
回首頁
切換:
標籤
|
MARC模式
|
ISBD
FindBook
Google Book
Amazon
博客來
New Advances in Spectroscopy: Applications to Aqueous Interfaces and Liquid Carbon.
紀錄類型:
書目-電子資源 : Monograph/item
正題名/作者:
New Advances in Spectroscopy: Applications to Aqueous Interfaces and Liquid Carbon./
作者:
Mizuno, Hikaru.
出版者:
Ann Arbor : ProQuest Dissertations & Theses, : 2021,
面頁冊數:
88 p.
附註:
Source: Dissertations Abstracts International, Volume: 83-03, Section: B.
Contained By:
Dissertations Abstracts International83-03B.
標題:
Chemistry. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28498644
ISBN:
9798535562919
New Advances in Spectroscopy: Applications to Aqueous Interfaces and Liquid Carbon.
Mizuno, Hikaru.
New Advances in Spectroscopy: Applications to Aqueous Interfaces and Liquid Carbon.
- Ann Arbor : ProQuest Dissertations & Theses, 2021 - 88 p.
Source: Dissertations Abstracts International, Volume: 83-03, Section: B.
Thesis (Ph.D.)--University of California, Berkeley, 2021.
This item must not be sold to any third party vendors.
This dissertation comprises two major projects. The first is the study of ions and molecules at the air/water interface using second-order nonlinear spectroscopy to measure interfacial electronic |χ(2)|2-spectra. The second is the investigation of the liquid state of carbon using time-resolved soft X-ray free electron laser spectroscopy.The nature of ions and molecules at and near aqueous interfaces is central in many chemical systems including atmospheric chemistry, electrochemistry, and biochemistry, but remains incompletely understood. Contrary to widely held earlier views, recent studies have unambiguously shown that some ions adsorb strongly to the air/water interface, with compelling evidence for enhanced surface concentrations of larger, more polarizable, weakly solvated anions. While the mechanism of selective ion adsorption has been shown to correlate strongly with ionic radii and hydration properties, considerable debate remains.In this dissertation, I describe the development and application of femtosecond broadband deep ultraviolet electronic sum frequency generation (DUV-ESFG) spectroscopy which allows quantitative analysis of peak positions, linewidths, and relative intensities that can be directly compared with theoretical calculations to yield new insights into the nature of ions and molecules at aqueous interfaces. Under the electric dipole approximation, the second-order nonlinear susceptibility vanishes in centrosymmetric media, and SFG spectroscopy is a surface-sensitive probe with a probe depth of ca. 1 nm, corresponding to a few outermost monolayers.In Chapter 2, I present the interfacial charge-transfer-to-solvent spectrum of thiocyanate (SCN−), a prototypical chaotropic anion, and discuss selection rules and salient differences between interfacial and bulk solvation that contribute to the observed spectral differences.In Chapter 3, we investigate the lowest energy charge-transfer-to-solvent bands of aqueous iodide using broadband DUV-ESFG and two-photon absorption spectroscopy and assign the observed transitions using atomic selection rules within a Rydberg transition model based on the jj-coupling limit. We find that DUV-ESFG signal at the air/water interface arises from symmetry breaking and solute-solvent vibronic coupling effects that relax the selection rules.In Chapter 4, we revisit the π→π* transition of the nitrite ion at the air/water interface and, together with MD simulations and electronic structure calculations, find no evidence of a previously reported contact ion pair induced redshift and strongly favorable bimolecular adsorption mechanism. However, the presence of a distribution of local solvation environments at the interface, including solvent separated ion pairs, solvent shared ion pairs, contact ion pairs, and small ion clusters is not ruled out.In Chapter 5, I present the |χ(2)|2-spectra of phenol at the air/water interface in the deep UV (5.4-6.3 eV) and find an apparent redshift of the electronic transitions relative to the bulk aqueous spectrum. MD simulations and electronic structure calculations suggest stabilization of the excited states due to the highly specific hydration structure effected at the interface. Additional work is ongoing to elucidate the role of selection rules and solvent environment on the observed spectral differences.In Chapter 6, I discuss my efforts to attempt heterodyne-detected DUV-ESFG spectroscopy and future directions, including incorporating a flat-jet that would enable measurements at low concentrations and liquid/liquid interfaces.The liquid state of carbon is of fundamental chemical significance and has potential practical applications, but it remains very poorly characterized. For example, studies suggest that carbon nanotubes and Q-carbon are formed through liquid intermediates. Moreover, novel carbon materials and routes for synthesizing them are of great interest, as some proposed carbon allotropes may have exciting new properties for technological applications, and better understanding of the liquid properties may suggest new routes for synthesizing them. In this dissertation, I present our recent efforts to characterize liquid carbon using pump-probe soft X-ray free electron laser spectroscopy at the carbon K-edge.In Chapter 7, I detail time-resolved resonant inelastic X-ray scattering (tr-RIXS) and X-ray emission spectra (tr-XES) of non-thermally melted carbon films measured at the Pohang Accelerator Laboratory X-ray Free Electron Laser in South Korea. An initial decrease in tr-RIXS signal intensity at short delay times was observed, corresponding to a decrease in the absorption cross-section of sp2-hybridized carbon atoms as structural reorganization occurs to form liquid carbon. Additional theoretical work is ongoing to further elucidate the dynamics of the melting and ablation processes.In Chapter 8, I present and discuss our recent attempts to demonstrate optical & soft X-ray sum frequency generation spectroscopy at the carbon K-edge, building upon soft X-ray second harmonic generation spectroscopy demonstrated by our group at FERMI in Italy.
ISBN: 9798535562919Subjects--Topical Terms:
516420
Chemistry.
Subjects--Index Terms:
Liquid state of carbon
New Advances in Spectroscopy: Applications to Aqueous Interfaces and Liquid Carbon.
LDR
:06317nmm a2200373 4500
001
2345139
005
20220531132447.5
008
241004s2021 ||||||||||||||||| ||eng d
020
$a
9798535562919
035
$a
(MiAaPQ)AAI28498644
035
$a
AAI28498644
040
$a
MiAaPQ
$c
MiAaPQ
100
1
$a
Mizuno, Hikaru.
$3
3684023
245
1 0
$a
New Advances in Spectroscopy: Applications to Aqueous Interfaces and Liquid Carbon.
260
1
$a
Ann Arbor :
$b
ProQuest Dissertations & Theses,
$c
2021
300
$a
88 p.
500
$a
Source: Dissertations Abstracts International, Volume: 83-03, Section: B.
500
$a
Advisor: Saykally, Richard J.
502
$a
Thesis (Ph.D.)--University of California, Berkeley, 2021.
506
$a
This item must not be sold to any third party vendors.
520
$a
This dissertation comprises two major projects. The first is the study of ions and molecules at the air/water interface using second-order nonlinear spectroscopy to measure interfacial electronic |χ(2)|2-spectra. The second is the investigation of the liquid state of carbon using time-resolved soft X-ray free electron laser spectroscopy.The nature of ions and molecules at and near aqueous interfaces is central in many chemical systems including atmospheric chemistry, electrochemistry, and biochemistry, but remains incompletely understood. Contrary to widely held earlier views, recent studies have unambiguously shown that some ions adsorb strongly to the air/water interface, with compelling evidence for enhanced surface concentrations of larger, more polarizable, weakly solvated anions. While the mechanism of selective ion adsorption has been shown to correlate strongly with ionic radii and hydration properties, considerable debate remains.In this dissertation, I describe the development and application of femtosecond broadband deep ultraviolet electronic sum frequency generation (DUV-ESFG) spectroscopy which allows quantitative analysis of peak positions, linewidths, and relative intensities that can be directly compared with theoretical calculations to yield new insights into the nature of ions and molecules at aqueous interfaces. Under the electric dipole approximation, the second-order nonlinear susceptibility vanishes in centrosymmetric media, and SFG spectroscopy is a surface-sensitive probe with a probe depth of ca. 1 nm, corresponding to a few outermost monolayers.In Chapter 2, I present the interfacial charge-transfer-to-solvent spectrum of thiocyanate (SCN−), a prototypical chaotropic anion, and discuss selection rules and salient differences between interfacial and bulk solvation that contribute to the observed spectral differences.In Chapter 3, we investigate the lowest energy charge-transfer-to-solvent bands of aqueous iodide using broadband DUV-ESFG and two-photon absorption spectroscopy and assign the observed transitions using atomic selection rules within a Rydberg transition model based on the jj-coupling limit. We find that DUV-ESFG signal at the air/water interface arises from symmetry breaking and solute-solvent vibronic coupling effects that relax the selection rules.In Chapter 4, we revisit the π→π* transition of the nitrite ion at the air/water interface and, together with MD simulations and electronic structure calculations, find no evidence of a previously reported contact ion pair induced redshift and strongly favorable bimolecular adsorption mechanism. However, the presence of a distribution of local solvation environments at the interface, including solvent separated ion pairs, solvent shared ion pairs, contact ion pairs, and small ion clusters is not ruled out.In Chapter 5, I present the |χ(2)|2-spectra of phenol at the air/water interface in the deep UV (5.4-6.3 eV) and find an apparent redshift of the electronic transitions relative to the bulk aqueous spectrum. MD simulations and electronic structure calculations suggest stabilization of the excited states due to the highly specific hydration structure effected at the interface. Additional work is ongoing to elucidate the role of selection rules and solvent environment on the observed spectral differences.In Chapter 6, I discuss my efforts to attempt heterodyne-detected DUV-ESFG spectroscopy and future directions, including incorporating a flat-jet that would enable measurements at low concentrations and liquid/liquid interfaces.The liquid state of carbon is of fundamental chemical significance and has potential practical applications, but it remains very poorly characterized. For example, studies suggest that carbon nanotubes and Q-carbon are formed through liquid intermediates. Moreover, novel carbon materials and routes for synthesizing them are of great interest, as some proposed carbon allotropes may have exciting new properties for technological applications, and better understanding of the liquid properties may suggest new routes for synthesizing them. In this dissertation, I present our recent efforts to characterize liquid carbon using pump-probe soft X-ray free electron laser spectroscopy at the carbon K-edge.In Chapter 7, I detail time-resolved resonant inelastic X-ray scattering (tr-RIXS) and X-ray emission spectra (tr-XES) of non-thermally melted carbon films measured at the Pohang Accelerator Laboratory X-ray Free Electron Laser in South Korea. An initial decrease in tr-RIXS signal intensity at short delay times was observed, corresponding to a decrease in the absorption cross-section of sp2-hybridized carbon atoms as structural reorganization occurs to form liquid carbon. Additional theoretical work is ongoing to further elucidate the dynamics of the melting and ablation processes.In Chapter 8, I present and discuss our recent attempts to demonstrate optical & soft X-ray sum frequency generation spectroscopy at the carbon K-edge, building upon soft X-ray second harmonic generation spectroscopy demonstrated by our group at FERMI in Italy.
590
$a
School code: 0028.
650
4
$a
Chemistry.
$3
516420
650
4
$a
Physical chemistry.
$3
1981412
650
4
$a
Barium.
$3
3560264
650
4
$a
Laboratories.
$3
531588
650
4
$a
Semiconductors.
$3
516162
650
4
$a
Adsorption.
$3
580046
650
4
$a
Fluorides.
$3
620981
650
4
$a
Energy.
$3
876794
650
4
$a
Potassium.
$3
3562093
650
4
$a
Hydration.
$3
738666
650
4
$a
Thin films.
$3
626403
650
4
$a
Optics.
$3
517925
650
4
$a
Asymmetry.
$3
3562922
650
4
$a
Cameras.
$3
524039
650
4
$a
Physics.
$3
516296
650
4
$a
Lasers.
$3
535503
650
4
$a
Experiments.
$3
525909
650
4
$a
Sodium.
$3
3562677
650
4
$a
Carbon.
$3
604057
650
4
$a
Solvents.
$3
620946
650
4
$a
Phenols.
$3
915439
650
4
$a
Light.
$3
524021
650
4
$a
Geometry.
$3
517251
650
4
$a
Interfaces.
$2
gtt
$3
834756
653
$a
Liquid state of carbon
653
$a
Solute-solvent vibronic coupling
653
$a
Carbon K-edge
690
$a
0485
690
$a
0494
690
$a
0791
690
$a
0605
690
$a
0752
710
2
$a
University of California, Berkeley.
$b
Chemistry.
$3
1674000
773
0
$t
Dissertations Abstracts International
$g
83-03B.
790
$a
0028
791
$a
Ph.D.
792
$a
2021
793
$a
English
856
4 0
$u
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28498644
筆 0 讀者評論
館藏地:
全部
電子資源
出版年:
卷號:
館藏
1 筆 • 頁數 1 •
1
條碼號
典藏地名稱
館藏流通類別
資料類型
索書號
使用類型
借閱狀態
預約狀態
備註欄
附件
W9467577
電子資源
11.線上閱覽_V
電子書
EB
一般使用(Normal)
在架
0
1 筆 • 頁數 1 •
1
多媒體
評論
新增評論
分享你的心得
Export
取書館
處理中
...
變更密碼
登入