Failure of the classical gas model

heat capacity The free-electron Fermi gas connement within crystal density of states function Paul exclusion principle Fermi energy Fermi distribution function

 Free electron gas model: application to a metal Fermi energy Heat capacity Electrical conductivity Successes and failures

Fermi energy estimation The total number of states from E = 0 to E = EF must be equal to the total number of electrons in the system: 32 23 V 2mE F 2 2 N e 3D: Ne = 2 EF = 3 2 2m V 3 A 2mE 2 N e 2 E F= 2D: Ne = 2 Am

For a 3D metal, there is typically one free electron for every atom, or in other words one electron for every (31010)3 m3 of volume (typical volume of a primitive unit cell) Ne 1 28 3 = 4 10 m EF = 4 eV 3 V 3 1010

Fermi energy estimation EF = 4 eV Comments: over 100 times kBT at room temperature step-like T=0 behaviour of Fermi function a good approximation Electrons at EF have velocities ~ 106 to 107 ms1 often useful to talk about the Fermi temperature E F = k BTF TF 50, 000 K
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When is a thin lm 2 or 3 dimensional? Lx Ly Lz

2 k x 2 + k y 2 + kz 2 E= 2m ny nz nx kx = , ky = , kz = Lx Ly Lz

The energy levels associated with different nx and ny values are more closely spaced than those associated with different nz values Electrons will ll levels with increasing n and n values while n = 1
x y z

D(E)

nz = 3 nz = 2 E

The nz = 2 level begins to be occupied when either the number of electrons or the temperature is increased sufciently
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Heat capacity In the classical gas every particle acquires extra thermal energy as the temperature increased, so every particle contributes to the heat capacity: 3 C = Nek B 2 In the Fermi gas, only electrons within kBT of EF acquire extra thermal energy is roughly a fraction T/T of the total number That F therefore expect3 T (T/TF~1/100 at room C = Nek B 2 TF temperature)
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Electrical conductivity In equilibrium we now have a picture of the electrons in a solid lling up allowed states in k space up to an energy EF: Apply an electric eld: Equation of motion is dp = eE dt dk eE or = dt since p = k

ky

kx

Electrical conductivity In equilibrium we now have a picture of the electrons in a solid lling up allowed states in k space up to an energy EF: Apply an electric eld: After a time t, an electron with wavevector k will acquire an extra eEt k from the eld: k = Electric eld causes all electrons to transfer from k-state to k-state, in unison

ky

kx

ky

kx E
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Electrical conductivity If the electrons were in a vacuum, or an innite, perfect crystal at absolute zero the Fermi sphere would continue to shift in this way forever as the electrons accelerated indenitely In a real solid it is assumed that the electrons scatter, on average, after a time ... so each electron acquires, on average eE k = ky

scattering kx

Electrical conductivity Now electrical conductivity is dened by the equation j = E and j = n e qv d (note: ne = Ne/V)

Here, vd is the drift velocity the extra velocity due to the eld, which is related to k by: n e e 2 E p k eE hence j = vd = = = m m m m nee2 = m
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nee2 = m Electrical conductivity This is exactly the same formula as for the classical gas model

BUT the mean free path will be different:

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nee2 = m Electrical conductivity In the classical model, the mean free path was calculated from mfp = vthermal electrons were assumed to move at the thermal velocity 1 3 mvthermal2 = k BT 2 2 3k BT1 2 vthermal = 10 5 ms1 m Remember this gave a mean free path ~ a lattice constant using a typical room temperature value of Note: the drift velocity caused by the electric eld is very small compared with this a few mm s1
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nee2 = m Electrical conductivity In the free-electron fermi-gas model, the velocity to use is the Fermi velocity 1 mfp = vF where mvF 2 = E F 2 2E F 1 2 vF = 10 6 ms1 m Consequently, the value of obtained from measurement of electrical conductivity gives a mean free path ~ 10 100 lattice constants.
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nee2 = m Electrical conductivity In the free-electron fermi-gas model, the velocity to use is the Fermi velocity 1 mfp = vF where mvF 2 = E F 2 2E F 1 2 vF = 10 6 ms1 m Furthermore, if we measure the low-temperature conductivity in very pure crystals, we get mfp ~ size of crystal scattering is from edges of crystal! WHAT HAPPENED TO SCATTERING FROM THE LATTICE?
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Consider the effect of applying a magnetic eld B to the electron gas. The electron has magnetic moment B and so the electrons gain additional energy BB depending upon whether their spin lies parallel or anti-parallel to B. B B D( EF )
EF D( E ) 2 B B D( E ) 2 EF EF

D( E )

D( E )

D( E )

D( E ) D( EF ) 2
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2 = m / B = B D( E F )

m = 2 B ( B B)

Successes and failures explains the small heat capacity with linear T dependence as observed predicts small contribution to paramagnetic susceptibility ("Pauli paramagnetism") in metals gives same (successful) formula for electrical conductivity as did the classical theory unexpectedly long mean free path (turns out to be correct though!) no explanation of insulators: insulators have no free electrons BUT
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BUT WHY?

 Free electron gas model: application to a metal Fermi energy Heat capacity Electrical conductivity Successes and failures

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