7.2 Experimental Observations . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
7.2.1 STM/S-DFT: GNR Edge and Defect Polarization . . . . 147
7.2.2 TEM: CN-Resolved C–C Bond Energy . . . . . . . . . . . 149
7.2.3 XPS: Core Level and Work Function . . . . . . . . . . . . . 150
7.3 BOLS-TB Formulation and Quantification . . . . . . . . . . . . . . . 151
7.4 ZPS: Monolayer Skin Entrapment and Defect Polarization . . . . 153
7.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
8 Hetero-Coordinated Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
8.1 Observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
8.2 BOLS-TB Formulation of the PES Attributes . . . . . . . . . . . . . 165
8.3 ZPS: Core Band Entrapment and Polarization . . . . . . . . . . . . . 167
8.3.1 Ag/Pd, Cu/Pd, Zn/Pd and Be/W Interfaces . . . . . . . . . 167
8.3.2 C/Si, C/Ge, Si/Ge, Cu/Si and Cu/Sn Interfaces . . . . . . 167
8.4 Energy Density, Cohesive Energy, and Free Energy . . . . . . . . 172
8.5 Catalytic Nature, Toxicity, Radiation Protectivity and
Mechanical Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
8.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
9 Hybridized Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
9.1 STS and IPES: Antibonding and Nonbonding States . . . . . . . . 181
9.2 ARPES: Holes, Nonbonding and Bonding States . . . . . . . . . . . 184
9.3 Coverage Resolved O–Cu Valence DOS Evolution . . . . . . . . . 188
9.4 DFT Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
9.4.1 O–Ti(0001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
9.4.2 N–Ti(0001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
9.4.3 N–Ru(0001) and O–Ru(1010) . . . . . . . . . . . . . . . . . . 192
9.5 XPS and ZPS: Core Level Entrapment and Polarization . . . . . . 193
9.5.1 O–Ta(001) and O–Ta(111) . . . . . . . . . . . . . . . . . . . . 193
9.5.2 Monolayer High-T C and Topological Edge
Superconductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
9.5.3 Other Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
9.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
10 Hetero- and Under-Coordination Coupling . . . . . . . . . . . . . . . . . . 205
10.1 Ti(0001) Skin and TiO 2 Nanocrystals . . . . . . . . . . . . . . . . . . . 205
10.1.1 Photoactivity of Defected TiO 2 . . . . . . . . . . . . . . . . . 205
10.1.2 XPS: Ti(0001) Skin 2p Band Shift . . . . . . . . . . . . . . . 206
10.1.3 ZPS: Defect-Induced Entrapment and Polarization . . . . 207
10.1.4 Defect Enhanced Photocatalytic Ability . . . . . . . . . . . 209
xx
Contents
7.2.1 STM/S-DFT: GNR Edge and Defect Polarization . . . . 147
7.2.2 TEM: CN-Resolved C–C Bond Energy . . . . . . . . . . . 149
7.2.3 XPS: Core Level and Work Function . . . . . . . . . . . . . 150
7.3 BOLS-TB Formulation and Quantification . . . . . . . . . . . . . . . 151
7.4 ZPS: Monolayer Skin Entrapment and Defect Polarization . . . . 153
7.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
8 Hetero-Coordinated Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
8.1 Observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
8.2 BOLS-TB Formulation of the PES Attributes . . . . . . . . . . . . . 165
8.3 ZPS: Core Band Entrapment and Polarization . . . . . . . . . . . . . 167
8.3.1 Ag/Pd, Cu/Pd, Zn/Pd and Be/W Interfaces . . . . . . . . . 167
8.3.2 C/Si, C/Ge, Si/Ge, Cu/Si and Cu/Sn Interfaces . . . . . . 167
8.4 Energy Density, Cohesive Energy, and Free Energy . . . . . . . . 172
8.5 Catalytic Nature, Toxicity, Radiation Protectivity and
Mechanical Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
8.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
9 Hybridized Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
9.1 STS and IPES: Antibonding and Nonbonding States . . . . . . . . 181
9.2 ARPES: Holes, Nonbonding and Bonding States . . . . . . . . . . . 184
9.3 Coverage Resolved O–Cu Valence DOS Evolution . . . . . . . . . 188
9.4 DFT Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
9.4.1 O–Ti(0001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
9.4.2 N–Ti(0001) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
9.4.3 N–Ru(0001) and O–Ru(1010) . . . . . . . . . . . . . . . . . . 192
9.5 XPS and ZPS: Core Level Entrapment and Polarization . . . . . . 193
9.5.1 O–Ta(001) and O–Ta(111) . . . . . . . . . . . . . . . . . . . . 193
9.5.2 Monolayer High-T C and Topological Edge
Superconductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
9.5.3 Other Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
9.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
10 Hetero- and Under-Coordination Coupling . . . . . . . . . . . . . . . . . . 205
10.1 Ti(0001) Skin and TiO 2 Nanocrystals . . . . . . . . . . . . . . . . . . . 205
10.1.1 Photoactivity of Defected TiO 2 . . . . . . . . . . . . . . . . . 205
10.1.2 XPS: Ti(0001) Skin 2p Band Shift . . . . . . . . . . . . . . . 206
10.1.3 ZPS: Defect-Induced Entrapment and Polarization . . . . 207
10.1.4 Defect Enhanced Photocatalytic Ability . . . . . . . . . . . 209
xx
Contents