The Need for Quantum Mechanics in Materials Science
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1 The Need for Quantum Mechanics in Materials Science VBS/MRC Need for Quantum Mechanics 0
2 Some Experimental Facts Regarding Metals Dulong-Petit Law High-Temperature Molar Specific Heat = 3R Atoms - Classical Oscillators (Kittel) VBS/MRC Need for Quantum Mechanics 1
3 Some Experimental Facts Regarding Metals Wiedemann-Franz Law: Ratio of thermal (κ) to electrical conductivities (σ) depends linearly on T κ/σ = (Const)T, (Const) watt-ohm/k 2 (Ashcroft-Mermin) VBS/MRC Need for Quantum Mechanics 2
4 Some Basics Electron charge (e), mass(m), number density(n) Newtons Law dp dt t time) = F (p momentum, F force, Force on a charged particle (q), (q = e for electron, E, B electric and magnetic fields) F = q(e + p m B) Current density j = en p m Conductivities: j = σe (Electrical), q = κ T (Thermal) VBS/MRC Need for Quantum Mechanics 3
5 Drudé Theory Early 19 th century Electrons treated as classical particles Electrons collide with atoms (and other electrons) About electrons (How to do this???) What do you expect? VBS/MRC Need for Quantum Mechanics 4
6 Drudé Model How to handle all the electrons? Relaxation time approximation: τ time in which an electron will definitely undergo a collision Drudé Equation p(t + dt) = = dp dt ( 1 dt ) (p(t) + F dt) τ }{{} prob. no coll. = p τ + F VBS/MRC Need for Quantum Mechanics 5
7 Drudé Model Over a long time t l, electrons attain drift velocity and do not accelerate Thus, 1 t l tl 1 t l 0 tl 0 dp dt dt = = 0 p dt = p d Drudé Equation gives drift velocity: p d = τf = v d = τ F (drift velocity) m VBS/MRC Need for Quantum Mechanics 6
8 Drudé Model Drift velocity in an electric field (F = ee) Current density Electrical conductivity v d = τe m E j = nev d = ne2 τ m E σ = ne2 τ m VBS/MRC Need for Quantum Mechanics 7
9 So What? The theory has a parameter τ How to calculate τ? Well, we don t know yet! And...so, what? Calculate relaxation times from conductivity measurements What do you think it will be? VBS/MRC Need for Quantum Mechanics 8
10 Relaxation Times Calculated relaxation times (Ashcroft-Mermin) VBS/MRC Need for Quantum Mechanics 9
11 Thermal Conductivity Concepts in Materials Science I Energy of an electron at temperature T, E[T ] = 3 2 k BT T(x v x τ ) T(x+v xτ ) v x τ v x τ A (one-d) body with a temperature gradient Magnitude of velocity (speed) in x direction = v x Heat flux from left to right = n 2 v xe[t (x v x τ)] Heat flux from right to left = n 2 v xe[t (x + v x τ)] VBS/MRC Need for Quantum Mechanics 10
12 Thermal Conductivity contd. Concepts in Materials Science I Net heat flux towards positive x axis q = n 2 v E x(e[t (x v x τ)] E[T (x + v x τ)]) = nv x T ( T 3nk 2 ) x = B τt T 2m x = n v 2 x }{{} k B T m E T }{{} 3 2 k B ( T x Thermal conductivity: κ = 3nk2 B T τ 2m VBS/MRC Need for Quantum Mechanics 11
13 And now, Wiedemann-Franz! Ratio of thermal to electrical conductivity κ σ = 3 2 ( kb e ) 2 T It is linear in T! It is independent of the metal! What about the constant (Lorentz number)? 3 2 ( kb e ) 2 = watt-ohm/k 2 Expt. value watt-ohm/k 2! Celebrations! VBS/MRC Need for Quantum Mechanics 12
14 There is just one more thing... Dulong-Petit say specific heat is 3R One mole of univalent metal contains one mole of ions and one mole of electrons Ionic specific heat = 3R Electronic specific heat = 3 R (ideal gas) 2 Total specific heat = 9 2 R 9 3 for usual values of 2, 3, 9! 2 Ok, turn the music down! VBS/MRC Need for Quantum Mechanics 13
15 Hall Effect B y z x E y j x Electric field applied in the x direction current flows j x Magnetic field B applied in the z direction An electric field E y develops in the y-direction VBS/MRC Need for Quantum Mechanics 14
16 Hall coefficient Hall Effect contd. R H = E y j x B Drudé value of Hall coefficient Concepts in Materials Science I (prove this!) R D H = 1 ne Independent of relaxation time! VBS/MRC Need for Quantum Mechanics 15
17 What about experiments? Concepts in Materials Science I Ratio of theoretical and experimental Hall coefficients (Ashcroft-Mermin) Ok for some metals, but suggests that electrons are positively charged in some metals! Oh, God! Stop the party! VBS/MRC Need for Quantum Mechanics 16
18 Conclusions...and then... Concepts in Materials Science I Classical theory is able to explain Wiedemann-Franz (Success!) Fails with specific heat (Ok, lets see!) Fails miserably with Hall coefficients (Surprise!) Well, we DO NEED Quantum Mechanics! VBS/MRC Need for Quantum Mechanics 17
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