Classica(on

of Solids
Many possible ways to classify solids. Weve discussed BLs and
symmetry. Could consider e.g., metallic, insulating, semiconducting,
etc. Here we choose to classify according to bonding forces (related
to configuration of valence electrons).
So, first review a little atomic physics
Periodic table
Generally quantum states of electrons in atom specified by four quantum numbers (Q#s)
(hydrogen atom). We begin with independent electron picture.

Spectroscopic notation
n = Princ. Q# :
1, 2, 3, .
l = Orbital Q# :
0, 1, 2, .. l < n
m = Azimuthal Q# : -l m +l (2l + 1 values)
= spin Q# :
1
(2 values)

s, p, d, f, g,

A given energy level Enlm depends rather strongly on n and l, but much more weakly
on m and . For a given l,m, the most tightly bound electron is the one with the lowest
possible value of n. Similarly, for given n,m, electron with the lowest possible l is bound the
most tightly. This behavior together with Pauli exclusion principle, permits one to establish
Rules for constructing atomic states. These rules (with some exceptions) allow one to
determine atomic ground states of the elements. (S-O interaction, exchange)

The Hydrogen Atom

Schroedinger Eq (one elec. In Coulomb Pot.).

1 2
1

u
1
2u 2m

(ru) 2
(sin ) 2 2
=
[ E V (r )]u
r r 2
r sin
r sin 2 2

where u( r, , ) = R( r )Y ( , ), and Y ( , ) = ( )( )

Eigenfunct. of L2
m
L2Y ( , ) = l (l + 1)2Y ( , ), and Y ( , ) = Pl (cos )eim , (l m )

Centrifugal Pot.

The Radial Eq.

d2
2m
l (l + 1)2
( rR) = 2 [ E V ( r )
]rR
dr 2

2mr r 2

Centrifugal Pot.

Q# s -- n,l,m

Eec9ve Pot.
Coulomb Pot.= - e2/r.

Z2
En = 13.6 2 eV
n

Hydrogen Atom Degeneracies

Energy Eigenvalues

mr e4
En = 2 2 , where n radial or principal Quantum Number
2 n

From the Series Solution

n = l + 1 + q, where q is an int eger in the series exp ansion.

In General,

n = l + t, where t is the # of terms in R( r ).

Clear that there are many possible combinations of l and t
yielding a given value of n -- degenerate states.

Example -- l = 1 with two term radial solution (n = 3) has same

energy as l = 2 with a 1 term radial solution (n = 3)
(u310 or u311 compared with u320, u32 1 or u32 2 in the previous slide)
The extra energy in the former case comes from k.e. (2 terms in radial w-f -The Wiggle effect), while in the latter case it comes from the larger centrifugal
potential (l = 2).

Atomic Physics
Identical Particles - How do we deal with many electrons in atoms?
Quantum Particles are Indistinguishable
Example -- Collision of two Electrons
A) Initially 1 and 2 far apart
can distinguish
B) During collision (A)
Indistinguishable
C) After Collision
Indistinguishable

2 or 1 ?

Interaction

1 or 2 ?

Two States differing only in the interchange of Identical Particles

are one and the same state Quantum Mechanically
Mathematically -- N particles
! ! ! --!symmetry of wavefunction under exchange
utot (r1, r2 , r3 ,.., rN ) = uT (1, 2, 3 ,..., N ) (Shorthand notation)
Interchange particles 1 and 2 ! uT (2, 1, 3 ,..., N )
For indistinguish. Particles must be same to within a phase factor

uT (2,1,3,.., N ) = AuT (1, 2, 3 ,..., N ): exchange again, uT (1, 2, 3 ,..., N ) = A 2uT (1, 2, 3 ,..., N )
A = +1

symmetric; A = -1

Antisymm.

Same state, so A2 = 1

Identical Particles (cont.)

Schroed. Eq. For several particles (1st approx: no interaction among particles)
# !2 2
&
2
%! ( "1 + " 2 ) +V (1) +V (2)(u(1, 2) = ET u(1, 2)
(Initially label particles and
$ 2m
'
introduce indisting. later)
separate variables (no coupling), uT (1, 2) = ua (1)ub (2)
Subst. in, divide by ua(1)ub(2)
2 2

+
V
(
1
)
2m 1
ua (1) = Ea ua (1)

2 2

+
V
(
2
)
2m 2
ub (2) = Ebub (2),

where ET = Ea + Eb

(Except for labels these are

same eq. ; e- f belong to
same set for each case.)

Therefore, total w-f for system (2 particles) can be constructed from two
indep w-f for a single particle (product) -- energy is sum of 2 single
particle energies

Impose indistinguishability (w-f must be either symm. or anti-symm.

Symmetric

1
[ua (1)ub (2) + ua (2)ub (1)]
uS (1,2) =
2
Anti symmetric
1
[ua (1)ub (2) ua (2)ub (1)]
u A (1,2) =
2

Note: in each w-f, one

particle is in state a (at x1 or
x2) and one is in state b (at
x1 or x2), but no way of
telling which is which!

Identical Particles (cont.)

Spin and the Pauli Exclusion Principle (all particles with half-integral spin
must have antisymmetric total w-f: elec., protons, neutrons,...)
Note: uA vanishes when both particles in same state, e.g.
1
[ua (1)ua (2) ua (2)ua (1)] 0 !!!
u A (1,2) =
2

No two spin-1/2 particles can

be in the same QM state
(identical Quantum numbers)

Pauli Exclusion Principle

Anti-symmetry requirement on total w-f means
Spatial part symmetric when spin part antisymmetric
Spin part symmetric when spatial part antisymmetric
Example (2-electrons):
Addition of two
spin angular momenta
Stot =0, Sztot=0
Stot = 1, Sztot=1, 0, -1

1
[ua (1)ub (2) + ua (2)ub (1)] 1 [(+)s1 ()s 2 ()s1 (+)s 2 ]
2
2
AntiSymm
Symm
1
[ua (1)ub (2) ua (2)ub (1)] [(+)s1 (+)s 2 ]
2
1
[ua (1)ub (2) ua (2)ub (1)] 1 [(+)s1 ()s 2 + ()s1 (+)s 2 ]
2
2
1
[ua (1)ub (2) ua (2)ub (1)] [() s1 ()s 2 ]
2

Singlet
(Stot = 0)
Deg. = 1

Triplet
(Stot = 1)
Deg = 3

Identical Particles (cont.)

Exchange

AS requirement
new kind of force ; electrons must move to
keep total w-f AS
different energy for singlet and triplet states

How ? Symm. spatial w-f -- particles closer together on average than for Antisymm.
Spatial w-f

larger Coulomb repulsion energy.

Can show that uAS (r2 ! r1 )2 uAS !"!! uS (r2 ! r1 )2 uS

Called Exchange because terms that contribute to difference in energy between Symm
and Antisymm states involve exchange of particles in the integral, e.g.
terms like
e2

ua (2)ub (1)
ua (1)ub (2)

r
2 1

Spin Dependence

comes from total antisymmetry requirement -- symmetric

spatial part w-f can only occur with antisymmetric spin part and vice versa.
For a given pair of single particle w- f s (ua and ub) symmetric spatial state
(Singlet) has higher (Coulomb) energy than antisymmetric spatial state (Triplet).
What about states involving same single particle w-f s?

Periodic Table
Ionization Potentials of the Elements
Large Dips in first ionization potential at
Z = 3, 11, 19, 37 and 55
Li

Na

Rb

Second Ionization Potential

Cs

First Ionization Potential

Large Maxima in second ionization

potential at Z = 3, 11, 19, 37 and 55
and Dips at Z = 4, 12, 20, 38 and 56
Be

Mg

Ca

Sr

Ba

Label electrons by n,l,m,s (indep. elect.)

Remember -- changing # of pos. charges

AND # of electrons!
Main effect (large dips) is related to n
(principle quantum #)
Shells
Lowest order effect within a shell is
additional Coulomb attraction.
Each time we have to put an electron
in the next n state, the energy
increases substantially, and the first
ionization potential decreases.

n=3

3s,3p,3d (18) = 2 +6 + 10

n=2

2s, 2p (8)

n=1

1s (2)

Periodic Table (cont.)

Hund s Rules (What happens within a shell? -- ground state configuration)
Given energy level, Enlms , depends strongly on n and l, but much less strongly on m
and s. l-dependence comes from screening of the attractive Coulomb potential by
other electrons. (doesn t exist in hydrogen: e.g. 3s, 3p, 3d states are degenerate
except for fine structure.)
For a given l, m, s the most tightly bound electron has the lowest n.
For a given n, m, s the most tightly bound electron has the lowest l.
Combine with Pauli principle (for a given n and l, the triplet (symmetric spin)
states have the lowest energy. Therefore, fill l-shells initially with all spin-up and
then with spin-down . Maximize M = mi . No two states can have the same set of
quantum # s, nlms)
Example: Consider a particular (l = 2) subshell (2l + 1)x2 = 10 states (holds 10
electrons) (l = 0, 1 subshells are at lower energy)
2 electrons

L = 3, S = 1 (M = m1 + m2 = 3; Ms = 1/2 + 1/2 = 1)

5 electrons

L = 0, S = 5/2 (M = 2 + 1+ 0 -1 -2 = 0; Ms = 5x(1/2) = 5/2)

10 electrons

L = 0, S = 0 (M = 0 + 0 = 0; Ms = 5/2 - 5/2 = 0)

Atomic and Molecular Spectroscopy

States of Two-electron Atoms (Two electrons outside closed shell)
Single particle labeling (e.g., 4s5p) inadequate:

Ideal LS coupling

S-O interaction, electrostatic/Pauli, orbit-orbit

interactions not accounted for.

Need to combine ang. mom. of 2

electrons to form resultant

J = L1 + S1 + L2 + S2

Two logical ways:

1) LS (Russel-Saunders) Coupling
(lighter elements, small S-O int.)


L = L1 + L2 ; S = S1 + S2

J = L+S
2) j- j coupling (heavier elements)


J 1 = L1 + S1 ; J 2 = L2 + S2

J = J1 + J 2

Exchange symm, AS
Straight
coul.repulsion
IS included

Spin-Orbit -- J;
smallest j lowest
energy

Largest L1L2 L
Lowest energy

Atomic Physics (2-Elec. Atoms Cont.)

Various Terms

u Largest -- Exchange (S =0, S = 1)

- Singlet -- Symm spatial w- f. On average electrons closer together -- larger
Coulomb repulsion -- larger energy (relative to direct coulomb repulsion)
- Triplet -- AS spatial w-f. On average electrons farther apart -- smaller coulomb
repulsion -- lower energy (relative to direct Coulomb repulsion)

u Next Largest -- Orbit- Orbit

Coulomb effect also -- ave. distance between electrons depends on relative
orientation of orbits (L1L2 = (1/2)[L2 - L12 - L22]) -- therefore depends on L. Largest
L has smallest energy -- keeps electrons farthest apart (not obvious).

u Smallest -- Spin-Orbit (E = L S)
(LS = (1/2)[J2 - L2 - S2]) so splitting depends on J (J = L+ S, L+ S - 1, .|L - S|).
Sign of -- turns out to be positive -- largest J has largest energy.

Notation (usually specify by 7 Q # s -- n1 , n2 , l1 , l2 , S, L and J)

Multiplicity

2S+1L
J

Orbital Ang. Mom.

in spectroscopic
notation

In spectroscopic
notation

Total angular
momentum

e.g.,4p4d 3F2

Classica(on of Solids
Pauli Principle: Remember it has to do with anti-symmetry requirement of
total wavefunction for Fermions, but for present purposes, just use it in the usual
elementary form: no more than one electron can occupy the same state as
specified by the Q#s (n, l, m, ).
Veried experimentally
Rules for constructing atomic configuration (shells) :
and theore9cally
I.

Make table: n + l as column increasing downward, and l as row increasing to right.

II. Allow correct number of blocks for each value of n = l(# of ways can get n + l = constant)
e,g,, n = l = 5
# of elec. That can be accommodated; for each value of l is
l = 3, n = 3
2(2l+1). m can take on values -l, -l + 1, -l + 2,0, 1, 2, +l,
l = 1, n = 4;
l = 0, n = 5
and for each l and m, has two possible values.
III. Fill in the blocks starting always at the top (lowest n + l value and proceeding right to left
in filling blocks as we go down (highest l for a given n+l is filled first lowest energy config.)

See next page

Classica(on of Solids and Periodic Table

Energy Ordering :

n.l

n + l

Designa(on

Capacity -2(2l+1)

6,2

6d

10 (trans. Elements)

5,3

5f

14 (ac9nides)

7,0

7s

6,1

6p

5,2

5d

10 (trans. Elements)

4,3

4f

14 (rare earths)

6,0

6s

5,1

5p

4,2

4d

10 (trans. elements)

5,0

5s

4,1

4p

3,2

3d

10 (trans. elements)

4,0

4s

3,1

3p

3,0

3s

2,1

2p

2,0

2s

1,0

1s

2 Shell

Shell
Shell

Lowest n + l rst,
Then highest l for
a given n + l

Classica(on of Solids and Periodic Table

Ordering of Configurations - start at upper left (lowest energy) proceeding right to left as go down
These are lowest energy configurations

n + l

0
(2)

1
(6)

2
(10)

[1s2] He
1s
[1s1] H

One block:
n=1, l = 0

[2s2]Be
2s
[2s1]Li

One block:
n=2, l=0

[3s2]Mg

3p
[4s2]Ca 4s [3s2,2p2]Si
[4s1]K
[3s2,3p1]Al

2p
3s
[3s1]Na
[2s2,2p1]B

4p
[5s1]Rb 5s [3d10,4s2,
4p1]Ga

[6s1]Cs

5p
6s [4d10,5s2,
5p1]In

[7s1]Fr

6p
7s [5f14,5d10,
6s2,6p1]Tl

3
(14)

4
(18)

Two blocks:
n=3, l=0
n=2, l=1
Two blocks:
n=4, l=0

n=3, l=1
Three blocks:
n=5, l=0
3d
n=4, l=1

n=3,
l=2
[4s2,3d1]Sc
Three b locks:
4d
n=6, l=0

n=5, l=1
[4d1,5s1]Sc
n=4, l=2
4f
5d



[5d1,6s2]La

Nota9on
(refers to outermost
occupied shell)

[nlN]

# of
Electrons
in lth state
Spectroscopic nota9on
Now make up usual
periodic table by plohng
n down, and # of val.
electrons more than a lled
shell to the right
n

S (2) p (6) 8 columns

Four blocks:
n=7, l=0
n=6, l=1
n=5, l=2
n=4, l=3

# of elec.
Beyond
lled shell

Classica(on of Solids and Periodic Table

Contracted Periodic Table

Lej out transi9on elements, rare earths and ac9nides for simplicity
#
n

H1s

He +

Li2s

Be2s2

B2p1

C2p2

N2p3

O2p4

F2p5

Ne2p6

Ne +

Na3s

Mg3s2

Al3p1

Si33p2

P3p3

S3p4

Cl3p5

Ar3p6

Ar +

K4s

Ca4s2

Ga4p1

Ge4p2

As4p3

Se4p4

Br4p5

Kr4p6

Kr +

Rb5s

Sr5s2

In5p1

Sn25p2

Sb5p3

Te5p4

I5p5

Xe5p6

Xe +

Cs6s

Ba6s2

Tl6p1

Pb6p2

Bi6p3

Po6p4

At6p5

Rn6p6

Rn +

Fr7s

Ra

II

III

IV

VI

VII

VIII
He1s2

Discussion: He, Ne, Ar, Kr, Xe and Rn are closed shell atoms (inert gases); outer elec. are 9ghtly bound

large ioniz. energies. Adding one elec. (and a proton) to these atoms leads to weak binding (Li, Na, K, Rb,
Cs, Fr have one elec. outside closed shell easy to detach --- very reac(ve materials. Conversely, atoms
with one elec. less than closed shell (Column VII F, Cl, Br, I, At) will bind an addi(onal electron very
(ghtly. (also very reac9ve)

Classica(on of Solids - bonding

Forma(on of Crystals in terms of decreasing bonding energy
Ionic Crystals: e.g,, LiF, NaCl, etc.

In such crystals Alkali atom (Li, Na, K, ) from Column I gives up an elec. to the halogen atom (Column VII),
e.g., F, Cl, Br, ).
Leaves (Alkali)+ and (Halogen)- ions: direct Coulomb forces hold crystal together.

V(r)

Core repulsion

Due to Pauli princ. and stable closed shell cong. of ions.

requires excess charge distribu(on introduced in
neighborhood of each ion by neighbor be accommodated
in unoccupied level. Large gap between occ. and unocc.
Levels costs a lot of energy to force ions together

r
Coulomb anrac9on
Covalent crystals: e.g., Ge, Si, etc.

Neighboring atoms tend to share electrons. Substan9al electron density between atoms. Shared
electrons must sa9sfy the Pauli principle. H2 molecule simplest example of covalent bond.
Covalent bonds very direc9onal and show strong angular proper9es; e.g., diamond structure (Si and Ge)
- nearest neighbors in tetrahedral coordina9on (corner atom and 4 nn along body diagonals. (look
at diamond structure. Bonds account for large resistance ot shear forces in these materials. Also usually
Poor conductors (electrons are localized and paired o). Each atom shares one of its outermost elec.
with each of its 4 nns. Therefore surrounding any atom, electrons form a closed shell (s2, p2 cong. sp
Hybrid wavefunc9ons) .

Classica(on of Solids - bonding

Metallic Crystals: e.g., Na, Al, Au, Fe)

Conduc9on electrons outside closed shell cong. (Na has one electron outside)behave as nearly free elec.
Become detached from atom, and wander throughout the crystal. These electron act as nega9vely
charged glue that holds posi9ve ions (on lahce sites) together. (A VERY SIMPLE MINDED AND
QUALITATIVE PICTURE. Usual bonding (ionic, covalent) is of no importance in such cases).

+
+

+
+

+
+

+
+

+
+

+
+

+
+

+
+

+
+

+
+

More or less uniformly

distributed electron density
- The nega9vely charged glue

+
+

+
+

Simple picture gives an inkling of why metals (mostly)( are duc9le and have high
electrical conduc9vi9es (more about this later).

Classica(on of Solids - bonding

Molecular crystals: e.g., A C H4 (bonding energies about 0.1 eV/Molecule)

Bonding forces are Van der Waals forces uctua9ons in 9me of electric dipole moment of one molecule
induces dipole m0oment in neighboring molecule, and these anract one another; ave. dip. Mom. is zero,
But at any instant there may be a net dipole moment.
Interac9on energy of tow neighboring dipoles is propor9onal to the product of the moments divided by
cube of distance separa9ng them. Very weak anrac9ve force. Simple Van der Waals crystals are rare gases
(inert gases Ar, Ne,) at very low temperatures.

Students read this sec9on in A&M