Flashcards in Beyond Free-Electron Theory Deck (27):

1

## What is an orbital?

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-in quantum mechanics, an atomic orbital is a wave function that describes the of either one or a pair of electrons in an atom

-atomic orbitals are designated by a combination of numerals e.g. 1s, 2p, 3d, 4f

-the numbers indicate the energy levels as well as relative distance from the nucleus

-the letters s, p, d and f designate the shape of the orbital, a consequence of the electron's angular momentum

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## Describe the s and p orbitals

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-s orbitals are spherical and centred on the nucleus, a 1s electron is almost entirely confined to a spherical region close to the nucleus, a 2s electron is restricted to a somewhat larger sphere

-a p orbital has the approximate shape of a pair of lobes on opposite sides of the nucleus

-an electron in a p orbital has equal probability of being found in either half

-no p orbitals exist in the first energy level but there is a set of three in each of the higher levels

3

## Describe the d and f orbitals

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-in all but the first two principal levels, there is a set of five d orbitals

-in all but the first three principal levels there is a set of 7 f orbitals

-all have complicated orientations

4

##
Radial Wave Functions for Outer Orbitals

d vs s & p

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-s and p levels extend much further away from the nucleus than d

-this means that the overlap with the next atom's orbitals will be much greater for s and p levels than for the d levels

5

## Pseudopotential

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-a potential wave function

-in this context it is used to remove oscillations of radial wave functions near the nucleus that are a computational inconvenience and have no real impact on calculations involving interaction between atoms

6

## Energy Level Scheme for Two Atoms at Equilibrium Separation

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-two isolated atoms are brought closer together

-they will reach an equilibrium separation distance where the force between the two atoms is zero

-the outer levels have overlapped, and when two wave functions overlap the two independent levels split into two new energy levels, one higher and one lower

-the magnitude of the split, the difference between the upper and lower energies is proportional to the overlap

-note that the lowest levels will not split as they do not overlap with the neighbouring atom

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## Energy Level Scheme - Adding More Atoms to the Model

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-if the separation is the same for each pair, then the splitting or bandwidth will be constant

-but the number of levels in the bandwidth will be equal to the number of atoms

8

##
Energy Level Scheme

Bragg Reflection

### -at critical k values Bragg reflection of electrons arises and these reflections interfere constructively with incident waves to produce standing waves

9

##
Energy Level Scheme

Gap

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-there are two forms of standing wave with squared modulus that will correspond to electrons accumulating wither between the atoms or sited on the atoms

-those sited on the atoms have lower energy so at the critical values of k, there will emerge a gap

-since the standing waves aren't propagating, group velocity is zero, they describe states that do not exist which is why the range of forbidden energies is called a gap

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##
Energy Level Scheme

Critical k values

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k = nπ/a

-where n is any positive integer

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## How to derive the critical k values?

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-consider a one dimensional chain of atoms bonded by the interaction between their potentials

-what happens to an electron trying to propagate through the chain of atoms

-treat each atom as a point scatterer and the electrons as plane waves

-using knowledge of x-ray diffraction in crystals realise there is an analogue to Bragg's Law, nλ = 2dsinθ byt for electrons in the crystal

-when the wavelength of the electrons matches the interatomic separation, Bragg reflection will occur:

nλ = 2a

-and since λ=2π/k :

k = nπ/a

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##
Brillouin Zone

Definition

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-the range of energies between the critical k values where Bragg reflection occurs

-i.e. the first Brillouin zone is the range of energies between the first two critical values of k

13

## Where are the gaps in relation to the Brillouin zones?

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-the gaps fall at zone boundaries, i.e. in between the Brillouin zones

-note that in general the gaps are not all the same size

14

## Shape of the Curve at the Zone Boundary

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-the definition of the group velocity:

vg = dω/dk

= 1/ℏ dE/dk

-so the group velocity is given by the tangent to the E(k) curve

-since the group velocity has to go to zero at the zone boundary (the states are standing waves at that point), the E(k) curve has to meet the zone at right angles

15

##
Effective Mass

Equation

### m* = ℏ² [d²E/dk²]^(-1)

16

##
The Kronnig-Penny Model

Description

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-replaces the real ionic potential with a series of wells and barriers

-the height of each barrier is Vo, the width of the well is a and the width of the barrier is b

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##
The Kronnig--Penny Model

Bloch's Theorem

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-the appropriate wave functions are clearly:

ψ(x) = Ae^(ikx) + Be^(-ikx) , 0

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##
The Kronnig--Penny Model

Boundary Conditions

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ψB(a):

Ae^(ika) + Be^(-ika) =

(Ce^(-κb) + De^(κb))*e^(iq(a+b))

ψ'B(a):

ikAe^(ika) -ikBe^(-ika) =

(-κCe^(-κb) + κDe^(κb))*e^(iq(a+b))

-we can solve this as a 4x4 determinant to find A, B, C, D

-we can then write the function that describes the energy levels as a function of q, the dispersion relation of the Kronnin-Penny Model

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##
The Kronnig-Penny Model

Dispersion Relation

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cos(q(a+b)) =

cos(ka)cosh(κb) + 1/2(κ/k - k/κ)sin(ka)sinh(κb)

-the LHS can only take values from -1 to +1

-and if we choose ka=nπ then the right hand side -> ±cosh(κb) but the magnitude of cosh(κb)>1 for all states in the well so there are no solutions for k=nπ/a

-which is what we found using the Bragg reflection argument

20

## How many states in the first Brillouin zone?

### 2N states exactly fill the first Brillouin zone

21

##
Brillouin Zones

Metals

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-since 2n states exactly fill the first Brillouin zone, we can infer that elements with odd valences will half fill Brillouin zones

-if the Fermi energy is halfway up the available states in a Brillouin zone, then there are many states immediately adjacent to Ef so the element is a metal

22

##
Brillouin Zones

Semiconductors and Insulators

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-even valence elements should fill the Brillouin zones

-these elements should be either insulators or semicondutors depending on the size of the gap

-e.g. Si and Ge are both semiconductors since they both have a valence of 4 and the gap is about 1ev or less

-they would be insulators if the gap was large enough

23

## Chemical Potential vs Fermi Energys

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-for metals, Ef lies at the top of a Brillouin zone

-for insulators or semiconductors 'Ef' lies halfway up the gap but by definition Ef separates the full and empty states and there are no no states in the gap

-this 'Ef' is actually the chemical potential, semiconductors and insulators don't really have an Ef although the term is sometimes used interchangeably with chemical potential

-for metals Ef = chemical potential since Ef lies at the zone boundary anyway

24

## Semimetal

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-there are exceptions to the odd valence = metal, even valence = insulator or semiconductor rule

-e.g. Ba has a valence of 2 and yet is a metal but not a good one

-the density of states at Ef is very low in Ba but there isn't a clear gap, and conductivity is lo hence the name semi metal

25

## Density of States and Band Structure

### -if you integrate the band structure or all values of k in 3D, you get the density of states

26

## How to split up the periodic table

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Group 1 - alkali metals, one valence electron, partially filled bands

Group 2 - even number of valence electrons but overlapping bands so metals

Group 4 - semiconductors, insulators, filled bands

Transition Metals

Noble Metals - one valence electron, partially filled bands so metals

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