Ch 6: Electronic Theory & Metals

Electronic Structure Theory

Hamiltonian and Density Functional method
Local Density Approximation
Jellium Model
Reasonable model for metals, with smeared ionic charge.
Electron density shows Friedel oscillations.
Electron Emission
Thermionic (hot) vs. Field (cold)

Page 1

Electronic Structure Theory: Hamiltonian

2
i

p
H

i 1 2m
R
N

Kinetic
Energy

i 1

Ze
1
e
r r 2 r r
ri rj
ri R
i, j

Ion-Electron
Coulombic Potential

Electron-Electron
Coulombic Potential

Hamiltonian that describes the surface electronic structure (ignoring ion motion).
Presence of electron-electron multi-body term makes solution intractable.
Page 2

Theory: Density Functional Method

Ion-Electron Term

Kinetic Energy

r
r
E n r K
n r

Ze
R

r
n r r
r r dr
r R

r
r
1 n r n r ' r r
r
r r drdr ' Exc n r
2
r r'
Ave. Electron-Electron Term

Exchange
Correlation Term

E[n(r)] gives ground state energy of the many-body problem given by previous
Hamiltonian.
Advantage of this formulation is that the density n(r) that minimizes E is found
by two coupled ordinary differential equations (see next slide).
Page 3

Theory: Density Functional Method

Eqn. #1: Schroedinger-like Equation

r
r
r
r
i r Veff r i r i i r
1
2

Eqn. #2: Effective Potential

r
n r ' r
r
r r dr ' Vxc r
r r'

1
r
2
Veff r Ze r r
r R
R
r
where n r i

These two coupled ordinary differential equations solves for (r) and
therefore give the electron density n(r) of the ground state.
Last exchange-correlation term Vxc requires an LDA approximation.
Page 4

Theory: Local Density Approximation

Inhomogenous

Homogenous

LDA approximates inhomogeneous electron density distribution at each

infinitesimal region with a locally homogeneous distribution, which is
exactly solvable for the exchange-correlation energy Vxc.
Page 5

Jellium Model: Basics

For simple metals, conduction electrons scatter weakly from screened
ion cores.
Replace ion cores with a uniform, positive background charge with
density nave equal to the spatial average of the ion charge distribution.
Charge density nave is expressed in terms of an inverse sphere
volume, 1/ nave = 4rs3/3, where rs = 2 to 5.
Electron density spills out at surface, creating a surface dipole.
Lower background ion densities (or higher rs values) give
smoother profiles.

Page 6

Jellium Model: Electron Density at Surface

r = 5 (low ion density)

r = 2 (high ion density)

Negative charge outside surface results in a surface dipole that holds in

electrons.
Electron density shows Friedel oscillations at surface, where electrons
attempt to screen abrupt ionic step function.
Page 7

Friedel Oscillations
+10 mV

-10 mV

A quantum corral of 60 Fe atoms assembled and viewed on Cu(001) by STM

at 4 K. (Eigler et al.)
Cu surface electrons form standing wave pattern inside corral, where Friedel
oscillations result from Fe atom defects.
Page 8

Jellium Model: Electron Density at Steps

Step
dipole
Surface
dipole
At steps, electrons form dipoles opposite to surface dipole and lower
the work function .
Page 9

Jellium Model: Work Function at Steps

Au

(ev)

Pt

Step Density (106/cm)

Work function decreases for vicinal surfaces with a higher step density.
Page 10

Electronic Structure: Definitions

V

V(z)

ave

V
Surface
Bulk
Dipole Chemical
Potential

Veff(z)

bulk

vacuum
Page 11

Electron Emission: Thermionic (Hot)

J T AT exp kT
2

Richardson-Dushman equation (1923) describes current density J emitted by

a heated filament, where plot of log(J/T2) vs. 1/T gives straight line.
Thermionic emitters such as pointed wires are used as electron sources in
devices such as oscilloscope, TV, TEM/SEM, etc.
Need low work function and high operating temperature, where tungsten
(4.5 eV) or LaB6 (2.5 eV) are typically used.
Alkali adatoms (Na, K, Cs) lower the filament work function and increase
emission.
Page 12

Electron Emission: Field (Cold)

J T AE exp B
2

3/ 2

E
xx

Fowler/Nordheim equation (1928) describes current density J emitted by a

filament under a high electric field, where plot of log(J/E2) vs. 1/E gives
straight line.
Field emitters such as Spindt tips are used as electron sources in flat panel
displays.
Page 13

Electron Emission: Field Emitter Examples

Spindt Cathode

Diamond-Like
Carbon (DLC)
Film

Page 14