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Electronic Band Structure of Solids Introduction to Solid State Physics   http://www.physics.udel.edu/~bnikolic/teaching/phys624/phys624.html
What are  quantum numbers? ,[object Object],Sommerfeld:   -vector (  is momentum) ,[object Object],[object Object],Bloch:   -vector (  is  the crystal momentum )  and  (the band index).
Semiclassical dynamics of Bloch electrons ,[object Object],[object Object],[object Object],[object Object]
What is the range of quantum numbers? ,[object Object],Bloch:  For each  ,  runs through all wave vectors in a single primitive cell of the reciprocal lattice consistent with the Born-von Karman periodic boundary conditions;  runs through an infinite set of discrete values.
What are the  energy levels? Sommerfeld: Bloch:   For a given band index n,  has no simple explicit form. The only general property is periodicity in the reciprocal space:
What is the velocity of  electron? Sommerfeld:  The  mean velocity   of an electron in a level with wave vector  is:  NOTE: Quantum mechanical definition of a mean velocity Bloch:   The  mean velocity   of an electron in a level with band index  and wave vector  is:  Conductivity of a perfect crystal:
What is the  Wave function Sommerfeld:  The  wave function of an electron with wave vector  is:  Bloch:   The  wave function   of an electron with band index  and wave vector  is: where  the function  has no simple explicit form. The only general property is its periodicity in the direct lattice (i.e., real space):
Sommerfeld vs.  Bloch : Density of States Sommerfeld  ->  Bloch
Bloch : van Hove singularities in the DOS
Bloch : van Hove singularities in the DOS of Tight-Binding Hamiltonian
Sommerfeld vs.  Bloch : Fermi surface ,[object Object],[object Object],No Fermi surface for insulators! Points of Fermi “Surface” in 1D
Sommerfeld vs.  Bloch : Fermi surface in 3D Sommerfeld:  Fermi Sphere Bloch:  Sometimes sphere, but more likely anything else For each partially filled band there will be a surface reciprocal space separating occupied from the unoccupied levels  -> the  set of all such surfaces  is known as the  Fermi surface  and represents the generalization to Bloch electrons of the free electron Fermi sphere. The parts of the Fermi surface arising from individual partially filled bands are  branches of the Fermi surface : for each n solve  the equation  in  variable.
Is there a Fermi energy of intrinsic Semiconductors? ,[object Object],[object Object]
DOS of real materials: Silicon, Aluminum, Silver
Colloquial Semiconductor “Terminology” in Pictures ← PURE DOPPED ->
Measuring DOS: Photoemission spectroscopy Fermi Golden Rule:  Probability per unit time of an electron being ejected is proportional to the  DOS of occupied electronic states  times the  probability (Fermi function)  that the state is occupied:
Measuring DOS: Photoemission spectroscopy Once the background is subtracted off, the subtracted data is proportional to electronic density of states convolved with a Fermi functions. We can also learn about DOS above the Fermi surface using Inverse Photoemission where electron beam is focused on the surface and the outgoing flux of photons is measured.
Fourier analysis of systems living on periodic lattice
Fouirer analysis of Schr ö dinger equation Potential acts to couple  with its reciprocal space translation  and the problem decouples into N independent problems for each  within the first BZ.
Fourier analysis, Bloch theorem, and its corollaries ,[object Object]
“ Free” Bloch electrons? ,[object Object],[object Object],[object Object],Bloch electrons in the limit  : electron moving through an empty lattice!
Schr ödinger equation for  “free” Bloch electrons Counting of Quantum States:   Extended Zone Scheme:  Fix  (i.e., the BZ) and then count  vectors within the region corresponding to that zone. Reduced Zone Scheme:  Fix  in any zone and then, by changing  ,  count all equivalent states in all BZ.
“ Free” Bloch electrons at BZ boundary
“ Free” Bloch electrons at BZ boundary ,[object Object]
“ Free” Bloch electrons at BZ boundary ,[object Object]
Extended vs. Reduced vs. Repeated Zone Scheme ,[object Object],[object Object]
Fermi surface in 2D for free Sommerfeld electrons
Fermi surface in 2D for “free” Bloch electrons ,[object Object],[object Object]
Fermi surface is orthogonal to the BZ boundary
Tight-binding approximation -> Tight Binding approach is completely opposite to “free” Bloch electron: Ignore core electron dynamics and treat only valence orbitals localized in ionic core potential.  There is another way to generate  band gaps   in the electronic DOS  -> they naturally emerge when perturbing around the  atomic limit .  As we bring more atoms together or bring the atoms in the lattice closer together, bands form from mixing of the orbital states.  If the band broadening is small enough, gaps remain between the bands.
Constructing Bloch functions from atomic orbitals
From localized orbitals to wave functions overlap
Tight-binding method for single s-band -> Tight Binding approach is completely opposite to “free” Bloch electron: Ignore core electron dynamics and treat only valence orbitals localized in ionic core potential.
One-dimensional case -> Assuming that only nearest neighbor orbitals overlap:
One-dimensional examples:  s-orbital band vs. p-orbital band
Wannier Functions -> It would be advantageous to have at our disposal localized wave functions with vanishing overlap  :  Construct Wannier functions as a Fourier transform of Bloch wave functions!
Wannier functions as orthormal basis set 1D example: decay as power law, so it is not completely localized!
Band theory of Graphite and Carbon Nanotubes (works also for  ): Application of TBH method  ,[object Object],[object Object],[object Object],Lattice structure of graphite layer: There are two carbon atoms per cell, designated as the A and B sublattices. The vector  connects the two sublattices and is not a translation vector. Primitive translation vectors  are   .
Chemistry of Graphite:  hybridization, covalent bonds, and all of that
Truncating the basis to a single  orbital per atom ,[object Object],[object Object],[object Object],[object Object],Eigenstates of translation operator: Bloch eigenstates:
Diagonalize 2 x 2 Hamiltonian
Band structure plotting: Irreducible BZ
Graphite band structure in pictures ,[object Object]
Graphite band structure in pictures:  Pseudo-Potential Plane Wave Method  Electronic Charge Density: In the plane of atoms In the plane perpendicular to atoms
Diamond vs. Graphite: Insulator vs. Semimetal
Carbon Nanotubes   ,[object Object],[object Object],[object Object]
From graphite sheets to CNT   ,[object Object]
Metallic vs. Semiconductor CNT ,[object Object],[object Object],[object Object],[object Object],Metallic 1D energy bands are generally unstable under a Peierls distortion  ->  CNT are exception since their tubular structure impedes this effects making their  metallic properties  at the level of a single molecule rather unique!
CNT Band structure

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Band structure(2)

  • 1. Electronic Band Structure of Solids Introduction to Solid State Physics http://www.physics.udel.edu/~bnikolic/teaching/phys624/phys624.html
  • 2.
  • 3.
  • 4.
  • 5. What are the energy levels? Sommerfeld: Bloch: For a given band index n, has no simple explicit form. The only general property is periodicity in the reciprocal space:
  • 6. What is the velocity of electron? Sommerfeld: The mean velocity of an electron in a level with wave vector is: NOTE: Quantum mechanical definition of a mean velocity Bloch: The mean velocity of an electron in a level with band index and wave vector is: Conductivity of a perfect crystal:
  • 7. What is the Wave function Sommerfeld: The wave function of an electron with wave vector is: Bloch: The wave function of an electron with band index and wave vector is: where the function has no simple explicit form. The only general property is its periodicity in the direct lattice (i.e., real space):
  • 8. Sommerfeld vs. Bloch : Density of States Sommerfeld -> Bloch
  • 9. Bloch : van Hove singularities in the DOS
  • 10. Bloch : van Hove singularities in the DOS of Tight-Binding Hamiltonian
  • 11.
  • 12. Sommerfeld vs. Bloch : Fermi surface in 3D Sommerfeld: Fermi Sphere Bloch: Sometimes sphere, but more likely anything else For each partially filled band there will be a surface reciprocal space separating occupied from the unoccupied levels -> the set of all such surfaces is known as the Fermi surface and represents the generalization to Bloch electrons of the free electron Fermi sphere. The parts of the Fermi surface arising from individual partially filled bands are branches of the Fermi surface : for each n solve the equation in variable.
  • 13.
  • 14. DOS of real materials: Silicon, Aluminum, Silver
  • 15. Colloquial Semiconductor “Terminology” in Pictures ← PURE DOPPED ->
  • 16. Measuring DOS: Photoemission spectroscopy Fermi Golden Rule: Probability per unit time of an electron being ejected is proportional to the DOS of occupied electronic states times the probability (Fermi function) that the state is occupied:
  • 17. Measuring DOS: Photoemission spectroscopy Once the background is subtracted off, the subtracted data is proportional to electronic density of states convolved with a Fermi functions. We can also learn about DOS above the Fermi surface using Inverse Photoemission where electron beam is focused on the surface and the outgoing flux of photons is measured.
  • 18. Fourier analysis of systems living on periodic lattice
  • 19. Fouirer analysis of Schr ö dinger equation Potential acts to couple with its reciprocal space translation and the problem decouples into N independent problems for each within the first BZ.
  • 20.
  • 21.
  • 22. Schr ödinger equation for “free” Bloch electrons Counting of Quantum States: Extended Zone Scheme: Fix (i.e., the BZ) and then count vectors within the region corresponding to that zone. Reduced Zone Scheme: Fix in any zone and then, by changing , count all equivalent states in all BZ.
  • 23. “ Free” Bloch electrons at BZ boundary
  • 24.
  • 25.
  • 26.
  • 27. Fermi surface in 2D for free Sommerfeld electrons
  • 28.
  • 29. Fermi surface is orthogonal to the BZ boundary
  • 30. Tight-binding approximation -> Tight Binding approach is completely opposite to “free” Bloch electron: Ignore core electron dynamics and treat only valence orbitals localized in ionic core potential. There is another way to generate band gaps in the electronic DOS -> they naturally emerge when perturbing around the atomic limit . As we bring more atoms together or bring the atoms in the lattice closer together, bands form from mixing of the orbital states. If the band broadening is small enough, gaps remain between the bands.
  • 31. Constructing Bloch functions from atomic orbitals
  • 32. From localized orbitals to wave functions overlap
  • 33. Tight-binding method for single s-band -> Tight Binding approach is completely opposite to “free” Bloch electron: Ignore core electron dynamics and treat only valence orbitals localized in ionic core potential.
  • 34. One-dimensional case -> Assuming that only nearest neighbor orbitals overlap:
  • 35. One-dimensional examples: s-orbital band vs. p-orbital band
  • 36. Wannier Functions -> It would be advantageous to have at our disposal localized wave functions with vanishing overlap : Construct Wannier functions as a Fourier transform of Bloch wave functions!
  • 37. Wannier functions as orthormal basis set 1D example: decay as power law, so it is not completely localized!
  • 38.
  • 39. Chemistry of Graphite: hybridization, covalent bonds, and all of that
  • 40.
  • 41. Diagonalize 2 x 2 Hamiltonian
  • 42. Band structure plotting: Irreducible BZ
  • 43.
  • 44. Graphite band structure in pictures: Pseudo-Potential Plane Wave Method Electronic Charge Density: In the plane of atoms In the plane perpendicular to atoms
  • 45. Diamond vs. Graphite: Insulator vs. Semimetal
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  • 48.