7Quantum theory: introduction and principle

Postulates of quantum mechanics:

The wavefunction

has all the information.

can be obtained from the Schrodinger equation,

^
H =E

The Born interpretation

2

is the probability density for finding a particle.

Acceptable wavefunctions
must be continuous, a continuous first derivative, be single-valued, and be squareintegrable.

 Observables
^

built from the position and momentum operators of the form

^x =x ^p x =

d
i dx

The Heisenberg uncertainty principle

[ ^ 1 , ^ 2 ]=^ 1 ^ 2 ^2 ^ 1 0

1 2

1
2

| [ ^ , ^ ] |
1

8Quantum theory: techniques and applications

Translational motion
Free motion in one dimension
2 d 2
=E
2 m d x2

The solutions of this equation have the form

= A e i kx +B ei kx

E=

k
2m

where A and B are constants.

all values of k are possible

the translational energy of a free particle is not quantized
In either case of

e i kx

or

ei kx

||

is independent of x

the position of the particle is completely unpredictable

A particle in a box

(a)

The acceptable solutions

The Schrodinger equation for the region where V = 0 is the same as for a free
particle, so the general solutions are given as:
k = A e i kx +B ei kx = A ( cos kx +isin kx ) + B ( cos kx +isin kx )=( A + B ) cos kx + ( AB ) isin kx

Then, with new coefficients

k =C cos kx + D sin kx E k =

k 2 2
2m

Boundary conditions
The wavefunction must be zero where V is infinite.
k ( x )=0

for the regions of

x0

and

x L

by the requirement of wavefunction continuity

k ( 0 )=0

and
and

k (L)=0
kL= 0
k ( L ) =Dsin

C=0

kL=n n=1, 2,

n ( x )=D sin( nx /L)n=1, 2,

En=n2 h 2 /8 m L2

Conclusion:
The need to satisfy boundary conditions implies that only certain
wavefunctions are acceptable, and hence restricts observables to discrete
values.

(b)

Normalization

The normalization condition:

L

d x=C 2 sin2
0

nx
L
d x=C2 =1
L
2

, so

2
L

1 /2

()

C=

The complete solution is

E n=

n 2 h2
n=1, 2,
8 m L2

n ( x )=

2
L

1/ 2

( )

sin(

nx
)
L

The energies and wavefunctions are labeled with the quantum number n.
A quantum number is an integer (in some cases, as we shall see, a half-integer)
that labels the state of the system.

(c)

The properties of the solutions

n
n

the number of nodes

has n -1 nodes

the number of nodes

the average curvature of the wavefunction

kinetic energy of the particle

Each wavefunction is a superposition of momentum eigenfunctions:

n ( x )=

2
L

1/ 2

( )

sin(

nx
2 2 ( i kx i kx )
n
)=
e e
k=
L
L
L

()

equal probability of travel to both directions

Because n cannot be zero, the possible lowest energy is

2

h
E 1=
2
8mL

This lowest, irremovable energy is called the zero-point energy.

The physical origin of the zero-point energy can be explained:
1. The uncertainty principle
a confined particle (some information for the position)
the momentum cannot be zero (precise value)
2. Acceptable wavefunctions
must be zero at both ends and need to be survived
must have curvature
nonzero kinetic energy

The separation between adjacent energy levels

2

( n+1) h
n2 h2
h2
En +1En=

=(2
n+1)
8 m L2
8 m L2
8 m L2

Separation

Separation

Separation

as
as
as

L
L

not quantized (like a free particle)

Corresponding principle
Classical mechanics emerges from quantum mechanics as high quantum
numbers are reached.
(d)

Orthogonality

Wavefunctions corresponding to different energies are orthogonal:

Suppose (for two different energies of
^
H n =En n

Then

En

and

Em

^
H m =Em m

^
H n d x=En m n d x

n ^H m d x=Em n m d x

Now consider (noting that energies are real)

m ^H n d x{ n ^H m d x } =En m n d xEm n m d x

Using hermiticity, the sum on the left is zero,

E
( nEm ) m n d x
0=

However, the two energies are different; therefore the integral on the right
must be zero:
m n d x=0

Motion in two and more dimensions

Schrodinger equation for a particle in a box in two dimensions:
2 2 2
+
=E
2 m x2 y 2

(a)

Separation of variables

Separation of variables technique

Divides the equation into two or more ordinary differential equations, one for
each variable
Write the wavefunction as a product of functions:
( x , y )=X ( x ) Y ( y)

With this substitution to the equation:

2 d 2 X
=E X X
2 m d x2
n ,n ( x , y )=
1

n x
n y
2
sin( 1 )sin( 2 )
1 /2
L1
L2
( L1 L2 )

n22 h 2
En ,n = 2 + 2
L1 L 2 8 m
1

n21

2 d 2 Y
=EY Y
2 m d y2

E=E X + EY

In same way, the solutions for a particle in a box in three dimensions:

n ,n ,n ( x , y , z ) =
1

n1

n2

8
L1 L2 L3
2

n3

h
En ,n , n = 2 + 2 + 2
L1 L2 L 3 8 m
1

1/ 2

sin(

n1 x
n y
n z
)sin( 2 )sin ( 3 )
L1
L2
L3

(b)

Degeneracy

When

L1=L2=L

in two-dimensional case;

n x
n y
2
n ,n ( x ) = sin ( 1 )sin ( 2 )
L
L
L
1

En ,n =( n21 +n 22)
1

h2
8 m L2

Consider the cases

n1=1, n2=2

and

2
x
2 y
1,2 ( x )= sin ( )sin(
)
L
L
L

5 h2
E1,2=
2
8mL

2
2 x
y
2,1 ( x )= sin (
)sin( )
L
L
L

5 h2
E2,1=
8 m L2

n1=2, n2 =1

Although the wavefunctions are different, they are degenerate.

The occurrence of degeneracy is related to the symmetry of the system.

Vibrational motion
Harmonic oscillation if the potential function is
1
V = kx 2
2

with restoring force

F=kx

(from

The Schrodinger equation becomes

2 d 2 1 2
+ kx =E
2 m d x2 2

F=dV /dx

The energy levels

The permitted energy levels are
1
k
=
2
m

( )

E = +

1 /2

( )

=0, 1,2,

Harmonic oscillator has zero-point energy;

1
E0=
2

Because the particle is confined, its position is not completely uncertain.

Therefore, its momentum cannot be exactly zero.
The particle fluctuates incessantly around its equilibrium position; though
classical mechanics would allow the particle to be perfectly still.

The wavefunctions
(a)

The form of the wavefunctions

The wavefunctions for a harmonic oscillator,

( x )=N ( polynomial in x ) ( bell-shaped Gaussian function )

1.

0 as x

2.

The exponent y is proportional to x ( mk )

1 /2

, so it decays more rapidly for large masses

and stiff springs.

3.It spread over wider range

as increases

Corresponding principle works at high

2

1/ 4

( )

( x )=N H ( y ) e y /2 y = =

mk

Rotational motion
Rotation in three dimensions: the particle on a sphere
A particle of mass m that is free to move anywhere on the surface of a sphere of
radius r.

(a)

The Schrodinger equation

The Schrodinger equation is

2 2
=E
2m

From Justification 9.7 (on p301)

1 2
2 mE
1
2
1

=
+
sin
2
2
2
2

sin sin
2

= =

2 IE
2
because I =mr
2

Two quantum numbers , lm l

l=0, 1,2, ml=l , l- 1, , - l +1, - l

Angular momentum quantum number

Magnetic quantum number

ml

The normalized wavefunctions and energies are

Y l ,m ( , ) :spherical harmonics (Table 9.3 on p302)
l

E=l ( l+1 )

l=0,1, 2,
2I

quantizedindependent of ml

( 2l+1 ) -fold degenerate

(b)

Angular momentum

Comparing with the classical rotational energy,

E=J /2 I

1/2

Magnitude of angular momentum={ l ( l+1 ) } l=0, 1,2,

z-co mponent of angular momentum=ml ml=l ,l - 1, , - l

The number of nodes in

Y l ,m ( , )
l

increases with

higher angular momentum implies higher kinetic energy

a high kinetic energy arises from the motion parallel to the equator
because curvature is greatest in that direction

(c)

Space quantization

For each

, there are only

2l+1

possible

ml

values:

The orientation of a rotating body is quantized: space quantization

The plane of rotation of a particle can take only a discrete range of
orientations.
Otto Stern and Walther Gelach (in 1921)
Experiment: Shot a beam of silver atoms through an inhomogeneous
magnetic field
Idea: A rotating, charged body behaves like a magnet and interacts with the
applied field

Expectation:
Classical mechanics:
Angular momentum can have all orientations:
the associated magnet can take any orientation
a broad band of atoms is expected
Quantum mechanics:
The angular momentum is quantized:
the associated magnet lies in a number of discrete orientations
several sharp bands of atoms are expected

Results:

Observed discrete band, and so confirmed the quantum mechanics.

(d)

The vector model

l x ,l y , and l z

are complementary observables:

[ l^ x , l^ y ]=i l^ z

[ l^ y , l^ z ]=i l^ x

[ l^ z , l^ x ] =i l^ y

And
[ l^ 2 , l^ q ] =0 q=x , y , and z

Although we can specify the magnitude of the angular momentum and any
of its component, if

lz

is known, then it is impossible to ascribe values to

the other two components.

8.1

Spin

Stern and Gelach observed two bands of Ag atoms in experiment:

Conflict with the fact that

must be an integer.

from spin, not due to orbital angular momentum

Spin:
Spin quantum number:
Magnitude: { s ( s +1 ) }

1/ 2

Spin magnetic quantum number:

ms=s , s - 1, , - s

Electrons have spin:

s=

1
2

Magnitude:

1 /2

1/ 2

{ ( )} ( )
1 1
+1
2 2

m s=

+1
( denoted as or )
2

m s=

1
( denoted as or )
2

3
=
4

The ground state configuration of Ag atom:

[ Kr ] 4 d10 5 s 1

, a single unpaired electron outside a closed shell

Particles:
Fermions: with half-integer spin
Electron, proton, neutron,
Bosons: with integer spin (including 0)
photon
Matter is an assembly of fermions held together by forces conveyed by bosons.

9Atomic structure and atomic spectra

The structure of hydrogenic atoms
Hamiltonian for hydrogenic atom
2

2
Ze
^
H=
e
2N
2 me
2m N
4 0r

(a)

The separation of variables

Divide Schrodinger equation into two parts:

1.The motion of the atom as a whole
2.The motion of electron relative to the nucleus

Schrodinger equation becomes:

2

2
Ze
1 1
1

=E = +
:reduced mass
2
4 0 r
me m N

Because potential energy is centrosymmetric (independent of angle),

we can write
( r , , )=R ( r ) Y ( , )

The equation does separate, we have to solve

2

Y =l ( l+1 ) Y
spherical harmonics: quantum number l , ml
2 d 2 u
+V eff u=Euu=rR
2 d r2
2

Z e2 l ( l+1 )
where V eff =
+
4 0 r
2 r 2

a particle of mass

in one-dimensional region where the potential

energy is Veff : radial wave equation

(b)

The radial solutions

2

Z e2 l ( l +1 )
V eff =
+
2
4 0 r
2 r

The 1st term:

Coulomb potential energy
The 2nd term:
stems from centrifugal force from the angular momentum of electron

Z e2 l ( l+1 )
V eff =
+
4 0 r
2 r 2

When

l=0

Electron has no angular momentum

Pure Coulombic and attractive at all radii

When

l 0

The centrifugal term is positive (repulsive)

As

r 0
V eff

, this repulsive term dominates the Coulombic term.

is repulsive

The allowed energies

2

Z e
En=
n=1, 2,
2 2 2 2
32 0 n

Radial wavefunctions have the form

R ( r )=( polynomial in r ) (decaying exponential in r )

Radial wavefunctions depend on both

l 2 l+1
/2
Rn ,l ( r )=N n ,l Ln +1 ( ) e

w here =

4 0 2
2 Zr
a0 =
=52.9 pm(Bohr radius)
n a0
me e 2
L ( ) :associated Laguerre polynomial

and

Interpretation of the radial wavefunction,

1.Exponential factor ensures that
2.The factor
3.

L( )

R (r ) 0

ensures that (provided

R (r)

as
l>0

R ( r )=0

at the nucleus.

oscillates and accounts for the presence of radial nodes.

9.1

Atomic orbitals and their energies

Atomic orbital:
A one-electron wavefunction for an electron in an atom
Defined by three quantum numbers:

n ,l , m | n ,l , ml
l

n , l, ml

Quantum numbers:
Principal quantum number:

n=1,2, 3,
Determine the energy of a hydrogenic atom
En=

Z 2 e 4
32 2 20 2 n2

Angular momentum quantum number:

l=0, 1,2, , n1
1/2

Magnitude of angular momentum={ l ( l+1 ) }

Magnetic quantum number:

ml

ml=l,l+1, ,l1, l
z-co mponent of angular momentum=ml

The value of the principal quantum number,

controls the maximum value of

controls the range of values of

Electron has its own spin:

ml

1
1
s= ms =
2
2

Need four quantum numbers

(n , l, ml , ms)

to specify

the state of an electron in a hydrogenic atom

(a)

The energy levels

Energy levels of hydrogenic atoms:

2

E n=

Z e
2 2 2 2
32 0 n

bound states : E< 0(cf . unbound states when E>0 not quantized )

E Z2

Rydberg constant:
H e4
hc R H =
H is the reduced mass for hydrogen.
32 2 20 2
4

RH=

H
m e
R R= 2 e 2 3
me
8 0h c

The only discrepancies arise from the neglect of relativistic corrections

(the increase of mass with speed).

(b)

Atomic orbitals

The ground state:

=

1
3 1 /2
0

( a )

1,0,0 |1, 0,0

er / a (for Z=1)
0

1 s orbital is spherically symmetrical .

maximum value of =

( a30 )

1/ 2

(at r=0)exponentially decays

Contributions of the potential and kinetic energy

Potential energy prefers to sit on the top of the nucleus.
Kinetic energy likes to be spread out uniformly.
A compromise between the two extremes:
The wavefunction spread away from the nucleus and has a reasonably
low average curvature.

9.2

Spectroscopic transitions and selection rules

Transition
i j E=h

Selection rule: a statement about which transitions are allowed

allowed or forbidden
Conservation of angular momentum:
A photon has an intrinsic spin angular momentum:

l= 1 for the transition of i j

s=1

 Quantum mechanical view: (Justification 10.4 on p335)

z ,fi = f z i d x= f | z|i
for one - electronatom
=e r with components :

After calculating

fi

x =ex , y =ey , z =ez

for all three components

fi 0 when l= 1 ml =0, 1

No restrictions for
momentum

, because it does not relate directly to angular

Grotrian diagram:
Summarizes the energies of the states and the transitions between them

The structures of many-electron atoms

The Schrodinger equation for a many-electron atom is highly complicated and no
analytical expression for the orbitals and energies can be given.
We are forced to make approximations.

Pauli principle:
When the labels of any two identical fermions are exchanged, the total
wavefunction changes sign; when the labels of any two identical bosons are
exchanged, the total wavefunction retains the same sign.
Pauli principle for two-electron total wavefunction:

( 1,2 )

( 2,1 )= (1,2 )

For two electrons, there are four possible spin states:

( 1 ) (2) ( 1) (2) (1) (2) (1) (2)

Because we cannot tell which electron is which (or there must be symmetry)
(1,2) (1) (2)
+(1,2)
( 1 ) (2)

Where

1 /2

(1,2)=( 1/2 )

{ ( 1 ) (2) (1) ( 2) }

(1,2)
( 2,1 ) =
+ ( 1,2 )
+ ( 2,1 ) =

Four possible total wavefunctions for the same special function

( 1 ) (2) (1 ) (2)
( 1 ) (2) (1) (2)

+
( 1 ) (2)

( 1 ) (2)

Only the last one satisfies the Pauli principle.

Any acceptable wavefunction for closed-shell species:

Slater determinant form:
( 1,2, , N )=

1
( N ! )1 /2

a ( 1) ( 1) a ( N ) ( N )

z ( 1) ( 1) z ( N ) ( N )

Antisymmetric under any exchange of any pair of electrons

(a)

Penetration and shielding

Effective nuclear charge:

Z eff =Z
where isthe shieldingconstant

The shielding constant is different for

s

and

electron has a greater penetration than a

p
p

electrons.
electron.(Fig 10.20 on

p340)
s

electron has less shielding than a

The energies of subshells depend on

s < p<d < f

electron.
l

, but not on

ml

Valence electrons:
Electrons in the outermost shell of an atom in its ground state
Responsible for the chemical bonds that the atom forms
(b)

The building-up principle

Building-up principle or Aufbau principle:

For an atom with atom number
Feed into the orbitals the
The order of occupation is:
1s2s 2 p3s3 p4 s3d 4 p5s 4d 6 s

electrons in succession.

Hunds maximum multiplicity rule:

An atom in its ground state adopts a configuration with the greatest number
of unpaired electrons
Spin correlation:
Electrons with parallel spins behave as if they have a tendency to stay well
apart, and hence repel each other less.

Consider (to satisfy the Pauli principle)

+ (1,2) a (1,2)
(1,2) p ( 1,2) 2 (1,2)=
1 (1,2)=
where ( 1,2 )=( 1/2 )

1/ 2

{ a ( 1 ) b (2) b ( 1 ) a (2) }

p ( 1,2 ) is parallel spin state

a ( 1,2 ) is paired spin state

When two electrons occupy at the same position,

vanishes while

survives

( 1,2 ) =( 1/2 )1 /2 { a ( 1 ) b ( 2 ) b ( 1 ) a ( 2) }

spin correlation

r 1=r 2

Electron configurations:
On average,

3d

3d

electrons are closer to nucleus than

4s

electrons.

electrons repel each other more strongly than the two

4s

electrons.
Sc has

[ Ar ] 3 d1 4 s 2

Cr and Cu have

[ Ar ] 3 d5 4 s 1

and

[ Ar ] 3 d10 4 s1

, respectively.

The subtle shades of energy differences and electron-electron repulsion

The rich-complexity of inorganic

d - metal

chemistry

 Calculations show that the energy difference between

depends on

[ Ar ] 3 d1 4 s 2

As

Z eff

[ Ar ] 3 d3

and

Z eff

increases, transfer of a

4s

electron to a

3d

orbital becomes

more favorable because electron-electron repulsions are compensated

by attractive interactions.

2+ : [ Ar ] 3 d 3
V

, the observed

Sc through Zn

[ Ar ] 4 s0 3 d n

configurations for

2+

cations of

The spectra of complex atoms

The actual energy levels are not given solely by the energies of the orbitals,
because the electrons interact with one another in various ways.

9.3

Singlet and triplet states

Singlet:
( 1,2 ) =( 1/2 )1 /2 { ( 1 ) ( 2 ) (1) ( 2) }

Triplet:
( 1) ( 2)
1
2

1
2

( ) { ( 1 ) ( 2 ) + ( 1 ) (2 ) }

+ ( 1,2 )=

(1) (2)

For states arising from the same configuration, the triplet state is generally lies
lower than the singlet state. The two states of

1 s 2 s He

differ by 6421 cm-1

(corresponding to 0.8 eV).

Two simple features in the spectrum of atomic He:
1. Only one electron is excited. Excitation of two electrons requires energy
greater than the ionization energy of the atom, so He+ ion is formed
instead of doubly excited atom.
2. No radiation transitions between singlet and triplet states.

9.4

Spin-orbit coupling

Spin-orbit coupling:
Interaction of the spin magnet moment with the magnetic field arising from the
orbital angular momentum

(a)

The total angular momentum

The energies of the levels with quantum numbers

s ,l , j

1
El , s , j= hcA { j ( j+ 1 )l (l+1 ) s ( s+1 ) }
2

The strength of the spin-orbit coupling depends on the nuclear charge.

The greater the nuclear charge, the stronger the spin-orbit interaction.

(b)

Fine structure

Fine structure:
The structure in a spectrum due to spin-orbit coupling
In Na, the spin-orbit coupling affects the energies by about 17 cm-1

9.5Term symbols and selection rules

(a)

The total orbital angular momentum

(b)

The multiplicity

(c)

The total angular momentum

Term symbol:
2 S+ 1

LJ

total orbital angular momentum quantumnumber , L

1 /2

magnitude : { L ( L+1 ) }
value : L=l 1 +l 2 ,l 1 +l 21, ,l 1l 2
L=0 1 23 4 5 6
L=S P D F G H I
a closed shell has a zero orbital angular momentum .
total spinquantum number , S

value : S=s 1 + s 2 , s1 + s2 1, ,s 1s2

multiplicity=2 S+ 1
total angular momentum quantum number , J
RussellSaunders coupling schem e :
I f the spin-orbit coupling is weak, then it is effective
only when all the orbital momenta are operating cooperatively

value : J=L + S , L + S1, ,LS

jj-coupling
Russell-Saunders coupling fails when the spin-orbit coupling is large (in
heavy atoms). In that case, the individual spin and orbital momenta of the
electrons are coupled into individual j values; then these momenta are
combined into a grand total J.
Correlation diagram :
The labels derived by using the Russell-Saunders scheme can be used to
label the states of the jj-coupling scheme.

(d)

Selection rules

Selection rules:
S=0 L=0, 1 l=1 J =0, 1, but J =0 | J =0

apply when RussellSuanders coupling is valid ( light atoms)

the quantumnumbers SL areill defined

as jjcoupling becomes more appropriate

transitions between singlettriplet states ( for which S= 1 ) ,

while forbiddenlight atoms , are allowedheavy atoms .