1.1 Overview
13
the amount of the CLS is proportional to the bond energy or the crystal potential
at equilibrium. Bond contraction and bond energy gain deepens the CLS for
the undercoordinated systems like atomic clusters, defects, solid skins. Bond
nature alteration determines the CLS for the hetero-coordinated systems such as
alloys, interfaces, dopants, embedded nanocrystals, and impurities. Polarization
of electrons splits and screens the local potentials, which shifts CLS negatively.
Therefore, CLS could be positive, negative, or their mixture.
(8) However, rules for the irregular coordination mediated valence DOS stay
unclear. The valence charge densification, localization, polarization, and transformation upon alloy and compound formation mediate the performance of
the substance such as the band gap, catalytic ability, electroaffinity, work
function, etc. The valance DOS evolution and the CLS are strongly correlated.
Therefore, a holistic exploration of both of them with quantitative derivative is
necessary [2].
1.2 Motivation and Objectives
Resolving the coordination-resolved, dynamic, local, and quantitative information
regarding the performance of bonds and electrons of the irregularly-coordinated
atoms remains as a “dead corner” though the interplay of STM/S, PES, and DFT
has advanced this subject area tremendously. Bond formation and relaxation and the
associated energetics, localization, entrapment, and polarization of electrons mediate
the electronic binding energy and the performance of a substance accordingly [1].
Therefore, one urgently needs to identify what “seeds” the STM/S signatures and
how the length and strength of the nearby bonds relax, which forms the subject of the
presented Electron Spectrometrics for the irregularly coordinated atoms, particularly.
This part aims to feature the development and applications of the coordinationresolved bond and electron spectrometrics with focus on the following:
(1) To combine the BOLS-NEP-TB notion [153], the enabled ZPS [8] and APECS
strategies towards comprehensive and quantitative information on the local
bonding and electronic dynamics.
(2) To clarify the rules and factors controlling the CLS and valence DOS evolution.
(3) To correlate the STM/S, PES, and AES attributes of a substance.
(4) To formulate the CLS dependence on local bond relaxation, quantum entrapment, and polarization.
(5) To quantify the local bond length, bond energy, BE density, atomic cohesive
energy, energy level of an isolated atom and its CN-resolved shift pertaining to
the irregularly coordinated atoms.
Consistent understandings gained insofar is very promising. It is clear that a perturbation to the Hamiltonian by bond contraction, bond nature alteration, and electron
polarization, dictates intrinsically and uniquely the energy shift of electrons in the
13
the amount of the CLS is proportional to the bond energy or the crystal potential
at equilibrium. Bond contraction and bond energy gain deepens the CLS for
the undercoordinated systems like atomic clusters, defects, solid skins. Bond
nature alteration determines the CLS for the hetero-coordinated systems such as
alloys, interfaces, dopants, embedded nanocrystals, and impurities. Polarization
of electrons splits and screens the local potentials, which shifts CLS negatively.
Therefore, CLS could be positive, negative, or their mixture.
(8) However, rules for the irregular coordination mediated valence DOS stay
unclear. The valence charge densification, localization, polarization, and transformation upon alloy and compound formation mediate the performance of
the substance such as the band gap, catalytic ability, electroaffinity, work
function, etc. The valance DOS evolution and the CLS are strongly correlated.
Therefore, a holistic exploration of both of them with quantitative derivative is
necessary [2].
1.2 Motivation and Objectives
Resolving the coordination-resolved, dynamic, local, and quantitative information
regarding the performance of bonds and electrons of the irregularly-coordinated
atoms remains as a “dead corner” though the interplay of STM/S, PES, and DFT
has advanced this subject area tremendously. Bond formation and relaxation and the
associated energetics, localization, entrapment, and polarization of electrons mediate
the electronic binding energy and the performance of a substance accordingly [1].
Therefore, one urgently needs to identify what “seeds” the STM/S signatures and
how the length and strength of the nearby bonds relax, which forms the subject of the
presented Electron Spectrometrics for the irregularly coordinated atoms, particularly.
This part aims to feature the development and applications of the coordinationresolved bond and electron spectrometrics with focus on the following:
(1) To combine the BOLS-NEP-TB notion [153], the enabled ZPS [8] and APECS
strategies towards comprehensive and quantitative information on the local
bonding and electronic dynamics.
(2) To clarify the rules and factors controlling the CLS and valence DOS evolution.
(3) To correlate the STM/S, PES, and AES attributes of a substance.
(4) To formulate the CLS dependence on local bond relaxation, quantum entrapment, and polarization.
(5) To quantify the local bond length, bond energy, BE density, atomic cohesive
energy, energy level of an isolated atom and its CN-resolved shift pertaining to
the irregularly coordinated atoms.
Consistent understandings gained insofar is very promising. It is clear that a perturbation to the Hamiltonian by bond contraction, bond nature alteration, and electron
polarization, dictates intrinsically and uniquely the energy shift of electrons in the