近幾年來，環境汙染一直是全球矚目的議題，空氣汙染更是許多環境汙染中最嚴重且致命的一種。由於快速成長地各種工業活動及過度使用的交通運輸工具，戶外空氣汙染已正式被世界衛生組織下的癌症研究中心宣告為致癌因子，其中以氣動粒徑在2.5微米以下之人為氣膠細懸浮微粒PM2.5對健康危害最鉅。氣膠懸浮微粒可以以不同的狀態存在，如極細微之固體或是液滴。氣膠的化學成分、物理尺寸形態以及結構對其物理、化學、生物以及光學特性都有直接的影響，因此，為了瞭解氣膠如何在各相關領域如環境化學與生物化學發揮其重要性及影響力，研究氣膠的基礎特性係當前至關緊要之課題。另一方面，水溶液介面在大自然中處處可見，因此在氣/液介面上的物理性質，例如: 表面水合結構、表面離子特性、表面pH值及有機溶質與水溶液間的交互作用，在許多重要研究領域，包括氣膠科學、大氣和海洋化學中皆扮演著重要的角色。對於在奈米尺度下的水溶液氣膠，由於其溶液介面具有較大的表面積與體積比，其氣/液介面的表面特性會更加顯著。為了暸解兩性有機溶質與水分子，在侷限空間的奈米水溶液氣膠中之交互作用以及相關的物理化學特徵，本篇論文首次利用氣膠真空紫外光光電子光譜 (Aerosol VUV Photoelectron Spectroscopy) 探討了苯酚和三個二羥基苯(Catechol, Resorcinol, Hydroquinone)異構物在奈米水溶液氣膠狀態下的價電子光電子光譜。利用這些酚類化合物的兩個具最低游離能的特徵峰，本論文探討了苯酚和二羥基苯在奈米水溶液氣膠狀態下之介面性質、溶劑水合結構及表面pH值等物理化學特性。同時藉由探測三個雙羥基取代苯的異構物，探討氫氧基團的數目及排列方式對酚類價電子能級結構及表面水合結構的影響。本論文對於含兩性有機成分之水溶液奈米氣膠在氣/液介面上的電子和水合結構等基礎性質以及其在大氣化學的重要性提供了較以往更為深入的了解。

Environmental pollutions have become the major issues of concern worldwide. Amongst, air pollution is the most severe and fatal pollution. Due to the rapidly growing industrial activities and excessively used transportations, outdoor air pollution has been officially announced by the International Agency for Research on Cancer (IARC) under the World Health Organization (WHO) as the carcinogenic factor. Anthropogenic particulate matters with an aerodynamic diameter smaller than 2.5 μm, are particularly harmful to human health. However, aerosol particulate matters can exist either as solid particle or as liquid droplets, The physical, chemical biological and optical properties of aerosols are directly influenced by the chemical composition, physical size and structures of aerosol. Therefore, to fundamentally understand how aerosols exert their crucial impacts in their various fields, including environmental chemistry and biochemistry, it is extremtly important to study the fundamental properties of aerosols. On the other hand, due to the ubiquitous existence of aqueous interfaces in nature, surface-specific characteristics at the aqueous solution/vapor interface, such as the solvation microstructures, surface propensity, surface pH and couplings between solutes and water have been the central concerns for numerous important fields, including the aerosol science, atmospheric/marine chemistry and electrochemistry. For nano-scaled aqueous aerosols, the surface-specific effects may become even more pronounced due to their large surface-to-volume ratios. To access the electronic and structural characters at/near the interface of amphiphilic organic-containing aqueous nanoaerosols, this thesis reports for the first time the valence electronic structures of phenol and three dihydroxybenzenes, including catechol, resorcinol and hydroquinone aqueous nanoaerosols via aerosol VUV photoelectron spectroscopy. By characterizing the two lowest vertical ionization energies for the chosen phenolic aqueous nanoaerosols, insights regarding their interfacial properties are unraveled. This thesis provides valuable information regarding the electronic and structural properties at/near the interface of amphiphilic organic-containing aqueous nanoaerosols. The implications of this study in aerosol science, atmospheric chemistry and biological science are also discussed.

Chapter 1 Introduction 1
1.1. Overview of aerosol science 1
1.1.1. Primary sources of aerosols 1
1.1.2. Fundamental characteristics of aerosols 3
1.1.2.1. Size effect of aerosols 3
1.1.2.2. Surface properties of aerosols 3
1.1.2.3. Electronic properties of aerosols 5
1.2. Implications of aerosols in the atmospheric and environmental chemistry 6
1.3. Implications of aerosols in the biomedical chemistry 7
1.4. Motivation and scope of this thesis 10
Chapter 2 Experiment 12
2.1. Principle of photoelectron spectroscopy 12
2.1.1. The photoelectric effect 12
2.1.2. Adiabatic and vertical ionization energy 14
2.2. Aerosol VUV photoelectron spectroscopy 15
2.3. Aerosol generation and beam formation via aerodynamic focusing 19
2.3.1. Atomizer and Adjustable aerodynamic lens system 19
2.3.2. The components of AADL system 22
2.3.3. Functions of AADL system 23
2.3.4. Characterization of AADL system 23
2.4. Ionization light sources of synchrotron radiation 25
2.4.1. VUV Synchrotron radiation introduction 25
2.4.2. Application and Advantage of synchrotron radiation 28
2.5. Detector of VUV photoelectron spectroscopy 29
2.6. Aerosol VUV photoelectron spectroscopy and the liquid microjet photoelectron spectroscopy comparison 31
2.6.1. Sample generation/introduction mechanism and size regime 31
2.6.2. The charging issue 32
2.6.3. Targets of interest and implications 34
2.7. Summary 35
Chapter 3 VUV photoelectron spectroscopy of Phenol and Phenolate Aqueous Aerosols 38
3.1. Introduction 38
3.1.1. The biological significance of Phenol and Phenolate 48
3.1.2. The atomospheric significance of Phenol and Phenolate 49
3.2. VUV photoelectron spectra of phenol and phenolate aqueous nanoaerosols 51
3.3. Segregation and partial hydration of phenol on the aqueous nanoaerosol interface 58
3.4. Co-existence of phenol and phenolate on the aerosol interface under high pH 64
3.5. Varying hydration extents of phenol and phenolate at the aqueous nanoaerosol interface 66
3.6. Determination of surface pH of nanoscaled aqueous aerosols 70
3.7. Summary 72
Chapter 4 Valence Electronic Structure of Benzendiols in Aqueous Aerosols 75
4.1. Introduction 75
4.1.1. Catechol 77
4.1.2. Resorcinol 78
4.1.3. Hydroquinone 79
4.1.4. Pyrogallol 79
4.2. VUV photoelectron spectroscopy of dihydroxybenzene aqueous nanoaerosols: Effects of -OH group arrangement 80
4.3. VUV photoelectron spectroscopy of dihydroxybenzene aqueous nanoaerosols: Effects of pH variety 84
4.4. Summary 92
Chapter 5 Conclusion 95

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