Electron and Phonon Spectrometrics

Preface
About This Book
Contents
About the Author
Nomenclature
Part I Electron Emission: Quantum Entrapment and Polarization
1 Introduction
	1.1 Overview
		1.1.1 Coordination Bonds and Energetic Electrons
		1.1.2 Challenges Faced by Existing Probing Technologies
		1.1.3 Known Mechanisms for Binding Energy Shift
	1.2 Motivation and Objectives
	1.3 Scope
	References
2 Theory: Bond-Electron-Energy Correlation
	2.1 Atomic Coordination Classification
	2.2 Core Band Energy Dispersion
	2.3 BOLS-NEP-LBA Notion
		2.3.1 Local Hamiltonian Perturbation
		2.3.2 BOLS-NEP Notion for the Undercoordinated Atoms
		2.3.3 Hetero-coordination: Entrapment or Polarization
		2.3.4 Generalization of the Irregular-Coordination Effect
	2.4 Valence Band and Nonbonding States
		2.4.1 Complexity of the Valence DOS
		2.4.2 Tetrahedral-Bonding Mediated Valence DOS
		2.4.3 Impact of Nonbonding States
	2.5 Numerical Strategies: Formulation and Quantification
		2.5.1 Irregular-Coordination Effect
		2.5.2 Local Energy Density and Atomic Cohesive Energy
	2.6 Summary
	References
3 Probing Methods: STM/S, PES, APECS, XAS, ZPS
	3.1 Energy Band Structure and Electronic Dynamics
	3.2 STM/S: Nonbonding and Anti-bonding States
	3.3 PES and AES: Valence- and Core-Band Shift
		3.3.1 General Description
		3.3.2 PES and AES
	3.4 APECS/XAS: Dual Energy-Level Shifts
		3.4.1 AES: Auger Parameter
		3.4.2 APECS: Dual-Level Shifts
		3.4.3 Extended Wagner Plots: Screening and Recharging
		3.4.4 XAS/XES: Dual-Level Resultant Shift
	3.5 ZPS: Atomic CN-Resolved Bond Relaxation
		3.5.1 Experimental and Analytical Procedures
		3.5.2 Quantitative Information
	3.6 Summary
	References
4 Solid and Liquid Skins
	4.1 XPS Derivatives
	4.2 BOLS-TB Formulation
	4.3 Registry and Sublayer-Order Resolution
		4.3.1 Fcc-Structured Al, Ag, Au, Ir, Rh, and Pd
		4.3.2 Bcc-Structured W, Mo and Ta
		4.3.3 Diamond-Structured Si and Ge
		4.3.4 The hcp-Structured Be, Re, and Ru
	4.4 Local Binding Energy Density and Atomic Cohesive Energy
	4.5 Summary
	References
5 Adatoms, Defects, and Kink Edges
	5.1 Observations
		5.1.1 XPS Detection
		5.1.2 STM Observation
	5.2 ZPS of Pt and Rh Adatoms: Catalytic Nature
	5.3 ZPS of Rh, W, and Re Kink Edges
		5.3.1 Atomic Arrangement at Edges
		5.3.2 Rh(110) and (111) Vicinal Edges
		5.3.3 W(110) Vicinal Edges
		5.3.4 Re(0001) and (12bar31) Kink Edges
		5.3.5 O-Re (12bar31) Kink Edge and Chemisorbed States
	5.4 Summary
	References
6 Atomic Chains, Clusters, and Nanocrystals
	6.1 Observations
	6.2 BOLS-TB Formulation
	6.3 Gold
		6.3.1 STM/S-DFT: End and Edge Polarization
		6.3.2 PES: The 4f and the 5d Bands
		6.3.3 BOLS-TB Quantification
	6.4 Silver
		6.4.1 STM/S-DFT: Adatom Polarization
		6.4.2 APECS: 3d and 5s Band Cooperative Shift
		6.4.3 BOLS-TB Formulation and Derivatives
	6.5 Copper
		6.5.1 STM/S-PES-DFT: Entrapment and Polarization
		6.5.2 APECS: Interface 2p and 3d Energy Shift
		6.5.3 BOLS-TB Formulation and Derivatives
	6.6 Nickel
		6.6.1 NEXAFS-XPS: Shell-Resolved Entrapment
		6.6.2 APECS: 2p and 3d Band Cooperative Shift
		6.6.3 BOLS-TB-ZPS Formulation and Derivatives
	6.7 Li, Na, K, Rb, and Cs Clusters and Skins
		6.7.1 Na 2p and K 3p Entrapment
		6.7.2 CN Dependent Binding Energy Shift
		6.7.3 Li, Na, K Skins and Size Trends
		6.7.4 Rb and Cs Skins and Size Trends
	6.8 Diamond Structured Si and Pb
		6.8.1 Entrapment of the 2p and the Valence Band of Si
		6.8.2 Pb 5d Binding Energy Shift
	6.9 Co, Fe, Pt, Rh, and Pd Nanocrystals
		6.9.1 Co Islands: Valence Entrapment
		6.9.2 Pd, Fe, Rh, and Pt: Core Level Entrapment
	6.10 STS of Si and Pd Nanostructures
	6.11 Summary
	References
7 Carbon Allotropes
	7.1 Introduction
		7.1.1 Wonders of CNTs and GNRs
		7.1.2 Challenges and Objectives
	7.2 Experimental Observations
		7.2.1 STM/S-DFT: GNR Edge and Defect Polarization
		7.2.2 TEM: CN-Resolved C–C Bond Energy
		7.2.3 XPS: Core Level and Work Function
	7.3 BOLS-TB Formulation and Quantification
	7.4 ZPS: Monolayer Skin Entrapment and Defect Polarization
	7.5 Summary
	References
8 Hetero-Coordinated Interfaces
	8.1 Observations
	8.2 BOLS-TB Formulation of the PES Attributes
	8.3 ZPS: Core Band Entrapment and Polarization
		8.3.1 Ag/Pd, Cu/Pd, Zn/Pd and Be/W Interfaces
		8.3.2 C/Si, C/Ge, Si/Ge, Cu/Si and Cu/Sn Interfaces
	8.4 Energy Density, Cohesive Energy, and Free Energy
	8.5 Catalytic Nature, Toxicity, Radiation Protectivity and Mechanical Strength
	8.6 Summary
	References
9 Hybridized Bonding
	9.1 STS and IPES: Antibonding and Nonbonding States
	9.2 ARPES: Holes, Nonbonding and Bonding States
	9.3 Coverage Resolved O–Cu Valence DOS Evolution
	9.4 DFT Derivatives
		9.4.1 O–Ti(0001)
		9.4.2 N–Ti(0001)
		9.4.3 N–Ru(0001) and O–Ru(10overline1 0)
	9.5 XPS and ZPS: Core Level Entrapment and Polarization
		9.5.1 O–Ta(001) and O–Ta(111)
		9.5.2 Monolayer High-TC and Topological Edge Superconductivity
		9.5.3 Other Surfaces
	9.6 Summary
	References
10 Hetero- and Under-Coordination Coupling
	10.1 Ti(0001) Skin and TiO2 Nanocrystals
		10.1.1 Photoactivity of Defected TiO2
		10.1.2 XPS: Ti(0001) Skin 2p Band Shift
		10.1.3 ZPS: Defect-Induced Entrapment and Polarization
		10.1.4 Defect Enhanced Photocatalytic Ability
	10.2 ZnO Nanocrystals Passivated with H, N, and O
		10.2.1 ZPS: Size-Induced Entrapment-Polarization Transition
		10.2.2 Band Gap, Work Function, and Magnetism
	10.3 Scratched SrTiO3 Skin: Defect States
	10.4 Summary
	References
11 Liquid Phase
	11.1 Wonders of H2O Molecular Undercoordination and Salt Hydration
	11.2 O:H–O Bond Oscillator Pair
		11.2.1 Basic Rules for Water
		11.2.2 O:H–O Bond Potentials and Cooperativity
		11.2.3 Specific Heat and Phase Transition
	11.3 Supersolidity and Quasisolidity
		11.3.1 Signatures
		11.3.2 Supercooling of Supersolid Phase
	11.4 Electron Spectrometrics
		11.4.1 STM and STS: Strong Polarization
		11.4.2 Water Skin: Entrapment and Polarization
		11.4.3 Ultrafast PES: Nonbonding Electron Polarization
		11.4.4 XAS: Supersolid Thermal Stability
	11.5 Proton Capture-Ability and Electron Emissibility of Halide Anions
	11.6 Perspectives
	References
12 Perspectives
	12.1 Advantages and Attainments
	12.2 Limitations and Precautions
	12.3 Prospects and Perspectives
Part II Electron Diffraction: Bond-Band-Barrier Transition
13 Introduction
	13.1 LEED, VLEED, STM/S, and PES
	13.2 O–Cu(001) Surface Reaction
	13.3 Objectives
	13.4 Scope
	References
14 Principles: Bond-Band-Barrier Correlation
	14.1 VLEED: Multibeam Resonant Diffraction
		14.1.1 Multi-Beam Diffraction
		14.1.2 Beam Interference
		14.1.3 Scattering Matrices and Phase Shift
		14.1.4 Multi-Atom Calculation Code
	14.2 Oxide Tetrahedron Bond Formation
		14.2.1 Observations
		14.2.2 Rules for Surface Bond Formation
		14.2.3 The Primary M2O Structure
		14.2.4 O–Cu(001) Bond Geometry and Atomic Valency
		14.2.5 Bond Geometry Versus Atomic Position
		14.2.6 Mechanism of Surface Reconstruction
	14.3 Valence Density-of-States
		14.3.1 O−1 Derived Three DOS Features
		14.3.2 O−2 Derived Four DOS Features
		14.3.3 Anomalous H-Bond like
	14.4 Energy-Dependent 3D-SPB
		14.4.1 Initiatives
		14.4.2 Complex Form of the Surface Potential Barrier (SPB)
		14.4.3 One-Dimensional SPB
		14.4.4 Energy Dependent 3D-SPB
		14.4.5 Parameterization and Functionalization
		14.4.6 Significance and Limitations of the 3D-SPB
	14.5 Summary
	References
15 Methodology: Parameterization
	15.1 Decoding Methodology
		15.1.1 Data Calibration
		15.1.2 Parameter Initialization
		15.1.3 Calculation Methods
		15.1.4 Criteria for Model Justification
	15.2 Code Validation
		15.2.1 Clean Cu(001)
		15.2.2 Oxygen on Cu(001): Model Comparison
	15.3 Cu3O2 Model Reality
		15.3.1 Numerical Quantification
		15.3.2 Physical Indication
	15.4 Summary
	References
16 VLEED Capability and Sensitivity
	16.1 Uniqueness of Solution
		16.1.1 ReV(z; z0, λ) Sensitivity
		16.1.2 ImV(z; z1, α) Correlation
		16.1.3 Solution Certainty
	16.2 VLEED Capacity and Reliability
		16.2.1 Decoding Procedures
		16.2.2 Sensitivity to the Bond Geometry
		16.2.3 Sensitivity to the SPB
	16.3 Summary
	References
17 Brillouin Zones, Effective Mass, Muffin-tin Potential, and Work Function
	17.1 Angular-Resolved VLEED Profiles
	17.2 Sharp Features: Brilliouin Zones and Energy Bands
		17.2.1 Brillouin Zones and Effective Electron Masses
		17.2.2 Lattice Reconstruction
		17.2.3 Valence Bands
	17.3 Bond Geometry, Valence DOS, and 3D-SPB
	17.4 Inner Potential Constant and Work Function
		17.4.1 Beam Energy Reduced V0
		17.4.2 Oxygen Reduced V0
		17.4.3 Oxygen Reduced Local ϕL(E)
	17.5 Mechanism Clarification
		17.5.1 Oxygen and Beam Energy Reduced V0
		17.5.2 Oxygen Reduced Local ϕL(E)
	17.6 Summary
	References
18 Four-Stage Cu3O2 Bonding Dynamics
	18.1 Exposure-Resolved VLEED: Four-Stage Reaction Kinetics
	18.2 Geometrical Examination
	18.3 Four-Stage Cu3O2 Bonding and Band Forming Kinetics
	18.4 Aging and Annealing Effects on VLEED Profiles
	18.5 De-Hybridisation of Oxygen
	18.6 Summary
	References
19 Perspectives
	References
Part III Multifield Phonon Dynamics
20 Wonders of Multifield Lattice Oscillation
	20.1 Scope
	20.2 Significance of Multifield Lattice Oscillation
	20.3 Outline of Experimental Observations
		20.3.1 Size Matter—Atomic Undercoordination
		20.3.2 Compression and Directional Uniaxial-Stain
		20.3.3 Debye Thermal Decay
	20.4 Overview on Theoretical Progress
		20.4.1 Quantum Size Trends
		20.4.2 Grüneisen Notion for Compression and Thermal Excitation
		20.4.3 Phonon Optical-Acoustic Thermal Degeneration
	20.5 Motivation and Objectives
	References
21 Theory: Multifield Oscillation Dynamics
	21.1 Lattice Oscillation Dynamics
		21.1.1 Single-Body Hamiltonian
		21.1.2 Atomic Chains
		21.1.3 Lagrangian Mechanics of Coupled Oscillators
		21.1.4 Collective Oscillation
	21.2 Taylor Coefficients Versus Observables
	21.3 Single Bond Multifield Oscillations
		21.3.1 Bond Length and Energy Relaxation
		21.3.2 Phonon Frequency Shift
	21.4 Formulation of Multifield Perturbation
		21.4.1 Atomic Undercoordination
		21.4.2 Thermal Excitation: Debye Thermal Decay
		21.4.3 Mechanical Compression: Elasticity and Energy Density
		21.4.4 Uniaxial Stretch: Single Bond Force Constant
	21.5 From Spectroscopy to Spectrometrics
	21.6 Summary
	References
22 Layered Structures
	22.1 Wonders of the 2D Structures
	22.2 Orbital Hybridization and Structure Configuration
		22.2.1 Phonon Frequency Tunability
	22.3 Numerical Reproduction of Phonon Relaxation
		22.3.1 Number-of-Layer Dependence
		22.3.2 Strain-Induced Phonon Softening and Band Splitting
		22.3.3 Mechanical Compression and Thermal Excitation
		22.3.4 Thermal Relaxation of Bandgap Energy
		22.3.5 Edge Discriminative Raman Reflectivity
	22.4 Summary
	References
23 Sized Crystals
	23.1 Skin Thickness of the Core-Shelled Structures
	23.2 Nanocrystals: Size and Thermal Effects
		23.2.1 Raman Shift of the Core-Shelled Crystals
		23.2.2 Skin Dominated Size Dependency
		23.2.3 Intergrain Interaction Derived THz Phonons
		23.2.4 Joint Effect of Size Reduction and Thermal Excitation
		23.2.5 Vibration Amplitude and Frequency of the Skin Atom
	23.3 Bulk Crystals: Compression and Thermal Excitation
		23.3.1 Group IV Semiconductors
		23.3.2 Group III-Nitrides
		23.3.3 TiO2 and ZnO
		23.3.4 Other Compounds
	23.4 Summary
	References
24 Water and Aqueous Solutions
	24.1 Water and Aqueous Solutions
	24.2 O:H–O Bond Segmental Cooperativity
		24.2.1 Physical Multifield Perturbation
		24.2.2 Acid, Base, Salt Solvation
	24.3 DPS of Water and Solutions
	24.4 Fraction of Bond Transition and Solute-Solute Interactions
	24.5 Surface Stress, Diffusivity and Viscosity
	24.6 Phase Transition by Compression and Ionic Polarization
		24.6.1 Spectrometric Varification
		24.6.2 Phonon Spectrometric Verification
	24.7 Summary
	References
25 Perspectives
	25.1 Attainments
	25.2 Perspectives
Appendix A Advantages and Limitations of the Electron and Phonon Spectrometrics
Appendix B Introduction of the “Spectral Studio” Analytical Package
References
Index