Rayleigh-Schrdinger Perturbation Theory

Introduction
Consider some physical system for which we had already solved the Schrdinger
Euation completely but then wished to perform another calculation on the same physical system
which has been slightly modified in some way! Could this be done without solving the
Schrdinger Euation again" This would be particularly ir#some if for e$ample all we wanted to
do was to sub%ect the system &which we now feel is well described by the wave functions and
energies' to a series of small changes such as imposing a series of electric or magnetic fields of
various strengths!
Suppose the original system were described by the hamiltonian H
(
) so that we had
a complete set of energy eigenvalues and eigenfunctions labelled by &('*
' ( &
+
' ( &
+
' ( &
+ (
E H
' ( &
,
' ( &
,
' ( &
, (
E H
&+'
' ( &
-
' ( &
-
' ( &
- (
E H

The modification of the system is described by the addition of a term V to the original
hamiltonian so that the new hamiltonian is H = H
(
. V and has solutions with unsuperscripted
symbols
+ + +
E H
)
, , ,
E H
etc!
Perturbation theory is based on the principle e$pressed in /c0aurin and Taylor
series that if a variable x is altered by a small amount then a function f&x + ' of the variable
can be e$pressed as a power series in ! Truncation of the series at the terms of different powers)

(
)
+
)
,
) defines the order of the perturbation as 1eroth) first) second order etc! So the
hamiltonian H and the general solution &
i
) E
i
' for the perturbed system are written as
V H H +
(
(2)
and the Schrdinger euation for the perturbed system is
+
i i i i
E V H H + ' &
(
&-'
where
+ + +
' , & , ' + & ' ( &
i i i i

and
+ + +
' , & , ' + & ' ( &
i i i i
E E E E
) ) )
' - & ' , & ' + &
i i i
are the +
st
-order) ,
nd
-order) -
rd
-order corrections to the i
th
state wave
functions2 ) ) )
' - & ' , & ' + &
i i i
E E E are the +
st
-order) ,
nd
-order) -
rd
-order corrections to the i
th

state energies!
Substituting for
i
and E
i
bac# into the Schrdinger euation &-' we have
' '& &
' '& &
' , & , ' + & ' ( & ' , & , ' + & ' ( &
' , & , ' + & ' ( &
(

+ + + + + +
+ + + +
i i i i i i
i i i
E E E
V H


( ) [ ]

+ + + + +
+ + + + +
' ( & ' , & ' + & ' + & , ' ( & ' + & ' + & ' ( & ' ( & ' ( &
' , & ' ( & ' , &
(
, ' + &
(
' ( & ' ( &
(
' &
' & ' &
i i i i i i i
i i i i i i
E V E E E E
E H H V H


&3'
which on euating the same powers of gives the euations
' ( & ' ( & ' ( &
( i i i
E H

(
1eroth order &same as ens! +'
' + & ' ( & ' ( & ' + & ' + &
(
' ( &
i i i i i i
E E H V + +

+
first order
' ( & ' + & ' + & ' ( &
(
' & ' &
i i i i
V E E H

+
first order &4'
' ( & ' , & ' + & ' + & ' , & ' ( &
(
' & ' &
i i i i i i
E V E E H +

,
second order &5'
and we could go on ! ! !
The 1eroth order euation tells us nothing new it6s %ust &+'! 7ut &4' and &5'
define the conditions of first and second order perturbation theory) which come ne$t!
+! 8irst order perturbation
&a' Energies
8or this we need e! &4'! 9e #now the sets :
i
&('
; and :E
i
&('
; but not the first-
order corrections li#e :
i
&+'
; so let<s e$press the latter as a combination of our basis set the
,
complete 1eroth order set of functions :
i
&('
;*
' ( &
' &
' + &
j
i j
j i
a

&='
Since
i
&+'
is a correction to :
i
&('
; the summation e$cludes j = i. Substituting &=' in &4' we get
( ) ( )
' ( & ' + & ' ( & (
(
' &
6
i i j i j
i j
V E E H a

and since) from &+') H

(

j
&('
> E
j
&('

j
&('
the operator H
(
in the last euation may be replaced by
E
j
&('
giving
' ( & ' + & ' ( & ( ' ( &
' & ' & 6
i i j i j
j
j
V E E E a

/ultiply by
k
&('
? and integrate*
The integral on the 0@S is the Aronec#er delta
kj
which means that it is unity if k = j
&normalisation' and zero otherwise &orthogonality'! Its effect in the summation is to #ill all the
terms for which j k) leaving

ki
) (
i
) (
i
) (
k k
E ) E E ( a
+ ( (
Bk|V|iC &D'
where BkEVEiC is a concise way of writing the integral
d V
i
* ) (
k

(
!
In &=' put i > k! This gives our first useful result*
E
i
&+'
> BiEVEiC &F'
In other words) the first order correction to the ith energy is the e$pectation value
d V
i i
' ( & ' ( &
?

of V obtained using the 1eroth order wave function

i
&('
! Gone of the other
functions
) (
i j
(

are involved! So the energy corrected to first order is %ust

i V i E E
i i
+
' ( &
&+('
&b' 9ave functions
-
Ge$t) try putting i k in &='! This provides the coefficient*
' ( & ' ( &
i k
k
E E
i V k
a

(11)
7ut this is what we need in &5' to e$press the first-order correction to the i
th
state wave function!
So the wave function of the i
th
state) corrected to first order) is
' ( &
' &
' ( & ' ( &
' ( &
k
i k i k
i i
E E
i V k

&+,'
Hnli#e the theory leading to the first-order energy E
i
in en! &F') in order to e$press the wave
function to first order the functions and energies
) (
i j
(

and
) (
i j
E
(

of all the other 1eroth-order

states are involved! The function in en! &=' is then normalised after calculating all the
coefficients e$pressed by en! &++'!
,! Second order perturbation
To second order the wave function
i
and the energy E
i
of the i
th
state are

i
>
i
&('
.
i
&+'
.
i
&,'

and E
i
> E
i
&('
. E
i
&+'
. E
i
&,'
Is was done to e$press the +st order corrections
i
&+'
to the wave functions in &=') we also write
the ,nd order corrections
i
&,'
to the functions as a linear combination
of the 1ero
th
order set:
i
&('
;*

' &
' ( & ' , &
i j
j j i
b
&+-'
and substitute this e$pression in &5'*
' ( & ' , & ' + & ' + & ' ( & ' ( &
' &
(
' & ' &
i i i i j i
i j
j
E V E E H b +

Is before we use e! &+'<s H

(

j
&('
> E
j
&('

j
&('
to replace H
(
by E
j
&('
) getting
' ( & ' , & ' + & ' + & ' + & ' ( & ' ( &
' &
' ( &
' &
i i i i i j i
i j
j j
E V E E E b +

/ultiply by
k
&('
? and integrate*
3
&Gote the Aronec#er deltasJ The one on the 0@S limits the summation to a single term*
) E E ( b
) (
i
) (
k k
( (

ki i i k i k i
E d V d E
' , & ' + & ' ( & ' + & ' ( & ' + &
? ? +

(14)
Kpting for k = i which we<ll call i) not only does the 0@S in &+3' become 1ero but so also does
the first term on the R@S because &=' e$pressed
i
&+'
in terms of all the
j
&+'
e$cept
i
&('
the
first R@S term is a
ki
where k i and is therefore 1ero! So we are left with
d V E
i i i
' + & ' ( & ' , &
?

in which
i
&+'
can be substituted from &+,') giving

) i ( k
) (
k
) (
i
) (
i
E E
i V k k V i
E
( (
,
&+4'
and so the perturbed energy level E
i
to second order is given by

+ +
) i ( k
) (
k
) (
i
) (
i i
E E
i V k k V i
i V i E E
( (
(
(16)

The ,
nd
order correction to the wave function)
i
&,'
) could be calculated in a similar
way to that in which we got
i
&+'
that led to &++'! This time it would be by opting for k i in
&+3') but we don6t do this here!
-
rd
order perturbation
@ere is the energy to -
rd
order*


+

+ +
i m i n
) (
n
) (
i
) (
m
) (
i
) i ( k
) (
k
) (
i
) (
i i
) E E )( E E (
i V n n V m m V i
E E
i V k k V i
i V i E E
( ( ( ( ( (
(
(16a)
(
th
order +
st
order ,
nd
order -
rd
order
correction correction correction
4
If you loo# at how the -
rd
order term is an e$tension of the ,
nd
order term you can guess how to
write any higher order terms! The
th
order correction to the energy would be

i m i n ! i n i m i i !

i
E E E E E E
i V ! n V m m V i
E
' & ' '& &
' ( & ' ( & ' ( & ' ( & ' ( & ' ( &
' &

(17)
Some points concerning Rayleigh-Schrdinger Pertubation Theory
+! Ilthough we stopped at second order) provided you were persistent enough there would be no
restriction to proceeding to as high an order of perturbation as you wished) using the euations
developed in the earlier part of this account! The energy interval LE
ik
in the denominators of the
correction terms &+() &+5' or &+=' show that successively higher order perturbations ma#e
successively smaller contributions!
,! Ill the r
th
-order corrections to the wave functions)
i
&r'
) and energies
i
&r'
) involve matri$
elements BkEVEiC of the perturbation operator V as in &+4' in the numerator and energy
differences
i
&r'

k
&r'
in the denominator) with the sole e$ception of
i
&+'
in &F'! Physically this
means that the procedure consists of mixing in functions into
i
&('
) particularly from the set of
high-energy unoccupied states
k
&('
!
-! 7ecause of the latter point) RS perturbation theory cannot be used if the state
k
&('
to be mi$ed
with
i
&('
is energetically degenerate to this state!
3! 8rom the perturbation corrections li#e those in ens! &+4' and &+5' the mi$ing in of higher-
order states ma#es the denominator negative! The effect is therefore to "tabi#ize the lower-
energy states!
4! Suppose that we were investigating the states of a molecule A that was influenced by
another molecule B at a distance $ from it! Then the perturbation operator V would consist of
those terms describing the coulomb attractions and repulsions of the particles of A with those of
B! The basis set of functions would be the complete set :
i
&('
; of functions for both molecules!
5
The e$pression for the perturbed energy states would start off li#e &+5' but would e$plore the
various orders until the higher-order terms become negligible! 9hen the successive terms
i
&+'
)

i
&,'
)
i
&-'
) ! ! ! are e$amined they are found to be of the forms $
+
) $
,
) $
3
) $
5
) $
D
) ! ! ! which
can be interpreted as the mutual interactions of the net charge) dipoles) uadrupoles) octupoles) !!!
&both permanent and induced' that are created on the two molecules! This result is sometimes
interpreted in terms of the non-bonded 0ondon or van der 9aals forces arising from the
fluctuating electronic charges on the molecules A and B! 9hile this description is a useful one)
you don<t need to thin# of fluctuating electronic charges Mintermolecular forces< are the
result of e$tending or Mperturbing< the hamiltonian of one molecule by the effect of the other!
The effect would also be described by a single calculation using a hamiltonian for the two-
molecule system!
Ipplications of Perturbation Theory
+! The electronic energy of the helium atom
The helium atom @amiltonian is
+, (
,
, (
,
+ (
,
,
,
,
,
3 3 3
' , &
,
' + &
, r
e
r
%e
r
%e
m m
H

+

,
_

i!e H > H
(
+ V
9e shall treat the electronic repulsion term as a perturbation V of the (
th
order
@amiltonian H
(
) so
+, (
,
3 r
e
V

&+D'
Zeroth order
Ignoring the electron-repulsion term &+D' we e$press H
(
as a sum of the two remaining
parts N one for each of the electrons &+' and &,'
H
(
> H
(
&+' . H
(
&,'
=
where H
(
&+' >
+ (
,
,
,
3
' + &
, r
%e
m

and H
(
&,' >
, (
,
,
,
3
' , &
, r
%e
m

These components H
(
&+' and H
(
&,' are each @amiltonians for @e
.
which is a Mhydrogen-li#e<
atom) whose Schrdinger euations are e$actly soluble*
H
(
&+'
(&)
&+' >
&('
&+'
H
(
&,'
&('
&,' >
&('
&,'
Remember N we #now
&('
and e$actly! The ground state is described by the hydrogenic +"
atomic orbitals

&('
>
' O e$p&
( +
a %r '
&+F'
>
( )
,
(
3 ,
3 ,
me %

&energy of Mthe @-li#e atom<'

9e write the complete (
th
order @amiltonian H
(
as H
(
&+),' as a reminder that it involves the
coordinates of both electrons and e$press the reuired ,-electron wave function
&('
&+),' as the
simple product

&('
&+),' >
&('
&+'
&('
&,'
Kperating on it with H
(
&+),' we have
H
(
&+),'
&('
&+),' > PH
(
&+' . H
(
&,'Q
&('
&+'
&('
&,'
> H
(
&+'
&('
&+'
&('
&,' . H
(
&,'
&('
&+'
&('
&,'
In the first term on the right hand side H
(
&+' operates on
&('
&+' giving
&('
&+' and leaving
&('
&,' unchanged! Similarly in the second term H
(
&,' operates on
&('
&,' giving
&('
&,' and
leaving
&('
&+' unchanged) so we have
H
(
&+),'
&('
&+),' >
&('
&+'
&('
&,' .
&('
&+'
&('
&,'
> ,
&('
&+'
&('
&,'
So the eigenvalue euation
H
(
&+),'
&('
&+),' > ,
&('
&+),'
D
tells us that the @e atom (
th
order energy is ,) i!e! twice the energy of the @e
.
ion! This is 43!3
eR so that the (
th
order energy is
E
&('
> +(D!D eR
This is physically meaningful because each of the two electrons is described as if it were
in a @e
.
atom) whose energy is ! The term
+, (
,
3 r
e

that accounts for their mutual repulsion

has been omitted to form H
(
! 7ut the energy is far too negative* the fact that the actual ground-
state electronic energy of @e is =F!( eR &the sum of the first two ioni1ation energies' shows that
it is essential to include the interelectronic repulsion term in the @amiltonian!
First order
8rom e! &F' the first order correction to the energy is E
+"
&+'
> B+"EVE+"C
' , & ' + & ' , ) + &
+
? ' , ) + &
3
' ( &
+,
' ( &
(
,
' + &

d d
r
e
E

Substituting for
&('
from &+F' and performing the integration leads to
E
&+'
> -3!( eR!
This brings the energy of helium to first order to
E > E
&('
. E
&+'
> +(D!D . -3!( > =3!D eR Pe$ptl! value =F!( eRQ
Second order
In order to form the matri$ elements
d V i V k
i k
' ( &
?
' ( &

reuired for substitution

in e! &+4' we need all the (
th
-order functions for
&('
) i!e!
) ) )
' ( &
,
' ( &
,
' ( &
+
+
! " "


and all the corresponding (
th
order energies
) ) )
' ( &
,
' ( &
,
' ( &
+
+
! " "
E E E
F
7ut these are #nown e$actly since they are the solutions of a hydrogen-li#e atom! Evaluation of
E
&,'
from es! &+4' and &+D' gives 3!- eR) so the energy of helium to second order is
E > E
&('
. E
&+'
. E
&,'
> +(D!D . -3!( 3!- > =F!+ eR Pe$ptl! value =F!( eRQ
Higher orders
The mi$ing of the higher order states
' ( &
k
into the ground state
' ( &
+"
should also include
the continuum) i!e! states with energies greater than 1ero &which is the ma$imum energy obtained
from the 7ohr formula
n
>
, ,
(
,
3 ,
, n
me %

'! The development of '

th
order perturbation theory is
tedious but routine) as is the numerical calculation of all the reuired matri$ elements!
Calculations have been performed up to +-
th
order giving
E > ,!F(-=,3-- hartree &atomic units of energy'
> =F!(+5+ eR
&E$ptl! value =F!( eR'
+(
,! Star# effect +* The shifting of the torsional energy levels of an K@ group by
an electric field!
Consider a part SK@ of a molecule in which the K@ group rotates around the
SK bond! K@ has an electric dipole moment whose component in the plane perpendicular
to the SK bond &rotation a$is' is ! &If
(
is the dipole moment along K-@ then

>
(
cos '
9hen an electric field F is applied in this plane &i!e! perpendicular to the rotation a$is') rotates
&in the xy plane' through a1imuthal angles monitored as so that successively comes into and
out of alignment with F. The coupling of the dipole with the field produces an energy
V&' > TF > ( cos
which is an energy perturbation term to the hamiltonian H
(
and is the component of the K@
bond dipole moment perpendicular to the rotation a$is! The total hamiltonian is
@ > H
&
. V !
In the absence of an electric field &F > (' the solution of the Schrdinger Euation describing the
internal rotation)
is the familiar one of a particle confined to a circle*
++
' ( & ' ( &
,
, ,
' ( & (
,

E
d
d
)
H

where
) ( m ) + t

) , t
! ! !
9e shall e$plore the perturbation of the torsional energy levels to second order by calculating
the matri$ elements of R that are reuired in the e$pression from en! &+4'*

+ +
' &
' ( &
6
' ( &
6 6
, ,
6 ,
m m
m m
m
E E
m V m m V m
m V m
)
m
E

&,('
7oth first- and second-order perturbation terms on the right of this euation reuire the matri$
elements V
mm*
where V
mm*
> Bm|V|m*C where m > m for the first-order and m m for the
second-order terms! 9e shall first evaluate the general matri$ element V
mm*
!
Substituting for
V > ( cos > ( U&e
i
. e
i
'
and the 1eroth order functions
m

im
e
,
+

the matri$ element V
mm*

6
m V m
becomes
V
mm*

d e e e e
(
d e e (
im i i im im im 6
,
(
6
,
(
' &
3
cos
,
+

+

3
(

1
]
1

+

+



,
(
,
(
' + 6 & ' + 6 &
d e d e
m m i m m i
+,

im
m
e
,
+
' ( &

)
m
E
m
,
, ,
' ( &

7oth integrals are of the form

d e
in

,
(
where n is an integer! Gow such an integral is 1ero
unless n > () in which case it is , &see footnote
+
'! Then as m = m t + either of the two integrals
contributes , and we have
( V
mm

,
+
6

&,('
This is our reuired non-1ero matri$ element of perturbation V! Gote that as V
mm
> ( there is no
first order correction to the energy!
9e can now calculate the second order perturbation term of the energy!
,
, , , ,
, +
) (
)
m
E
m



!
,
, ,
(
,
(
+
) (
E


Rotational level m > ( of the rotor is therefore lowered by a uantity proportional
to the suare of the field intensity and of the dipole moment of the K@ bond! The ,-
fold degeneracies of the levels are not lifted! &7ut they are when higher-order
perturbation theory is appliedJ'! Recall that is the component of the K@ bond dipole
moment perpendicular to the rotation a$is) and we should write
9hat if the field were applied in a direction other than perpendicular to the
torsional a$is" Then V > TF would have components V
z
and

V
x
from the couplings
along and perpendicular to the this a$is! The shift from

V
x
would be of the same form as
the one we %ust calculated &but smaller because F has a smaller component in the circle
+
If n () [ ] [ ] [ ] ( + ( +
+
, sin , cos
+ +
,
(
,
(
,
(
+ +

in
n i n
in
e
in
d e
in in

Ktherwise &n > (')

,
,
(

d
+-
' ( &
+
' ( &
(
' ( &
+
' ( &
(
' , &
(
( + + ( ( + + (

E E
V V
E E
V V
E
around which the dipole moment is rotating') and V
z
would be ( cos where is the
&constant' angle between and F!
If the electric field were applied !ara##e# to the rotational a$is) would still go
from ( to , but as it rotated) the K@ bond dipole would ma#e a constant angle with the
field! The energy shift would then be simply V ( sin where sin is the angle made
by the bond dipole with the torsional a$is &and the electric field'!
+3
-! Star# effect ,* Wegenerate perturbation theory!
Energy splittings in the @ atom
9e perturb the (
th
order hamiltonian @
(
of the @ atom by adding to it a term
V = e(z
Since z is antisymmetric &or odd' any diagonal matri$ element V
mm
is 1ero i!e!
(
?

+

dz z
m m

!
8or this reason there is no Star# effect to +
st
order PT!
In order to go to higher order we must form off-diagonal matri$ elements V
mn
! These
elements will couple the +" ground state
' ( &
+"
to higher states such as
' ( &
,"
)
' ( &
,
+ +
!

)
' ( &
,
(
!

)
' ( &
+ , !

which will result in a "+ifted energy level of what was the ," ground state) but since this
state is non-degenerate there will be no Star# "!#itting!
9e therefore ma#e the problem more interesting by replacing the ground state by the n >
, state spanned by the four functions ,") ,!
.+
) ,!
(
) ,!
-+
! 9e should li#e to #now to what e$tent
this 3-fold degeneracy is removed by the Star# effect!
Xeroth order functions
The four basis functions of the n > , shell of the @ atom) and their energies &all eual)
E
n>,
' are #nown e$actly! The functions can be written as products of functions involving
spherical coordinates r) - in the form R&r' &' &') and the only factor of these which
will concern us will be &' which is of the form e
im
where m > ( for ,s and +) () +
respectively for ,!
++
) ,!
(
) ,!
+
! 9ritten this way these functions are obviously eigenfunctions of
the angular momentum operator l
z
>

with eigenvalues m !
" &."' >
."
e
i&
l
z
&."' > ( &."'
!
.+
&.!
.+
' >
.!
e
i
l
z
&.!
++
' > .+ &.!
.+
'
!
(
&.!
(
' >
,!
e
i&
l
z
&.!
(
' > ( &.!
(
'
!
-+
&.!
+
' >
.!
e
i
l
z
&.!
+
' > + &.!
+
'
where
."
and
.!
are the parts of the ," and ,! IK functions without the &' factor!
+4
The reason that these functions are eigenfunctions of l
z
is because this operator commutes with
the hamiltonian! 7ut as l
z
also commutes with the perturbation term V = ez) matri$ elements
V
mm*
formed from functions functions
m
and
m*
corresponding to different angular momenta
m and 6 m are 1ero)
i!e! if Bil
1
jC > ( then BiV jC > ( also!
This is because) as l
z
is a hermitian operator its eigenfunctions are orthogonal if they belong to
different eigenvalues) i!e! matri$ elements Bm| l
z
|mC > (! The only non-1ero elements of V
are for basis functions corresponding to the same eigenvalue of l
z
. @owever) for the same
reason as in the application of perturbation theory of a Star# electric field to a molecular torsion)
diagonal matri$ elements of V are 1ero because the perturbation V = e(z) is not totally
symmetric) i!e! Bm|V|mC > ( for all |mC!
So we have the following!
(a) Ill diagonal elements of V are 1ero
(b) Gon-1ero elements of V must be from pairs of functions corresponding to the same
eigenvalue of l
z
.
This leaves only one pair of functions that forms a non-1ero element with V* that between ," and
,!
&
! Since their degeneracy does not allow them to be used in perturbation theory we shall need
to calculate the eigenvalues of the energy matri$ of V spanned by the four basis functions
&") !
++
) !
(
) p
+
'
Ill the elements of V will be 1ero e$cept two) those formed by &," and ,!
(
') and by &,!
(
and ,"'!
The 1eroth order energy E
&('
is the energy of the ," and ,! orbitals &all four have the same
energy) because for all hydrogen-li#e atoms with one electron) a subshell with principal uantum
number n is n
,
-fold degenerate! The perturbation energy matri$ V is therefore

V >
1
1
1
1
]
1

( ( ( (
( ( ( (
( ( (
( ( (
(
(
" V !
! V "
The complete hamiltonian matri$) H > H
0
. V is therefore
+5
H >

,
_

' ( &
,
' ( &
,
' ( &
,
' ( &
,
( ( (
( ( (
( ( (
( ( (
E
E
E
E
.

,
_

( ( ( (
( ( ( (
( ( (
( ( (

>

,
_

' ( &
,
' ( &
,
' ( &
,
' ( &
,
( ( (
( ( (
( (
( (
E
E
E
E

where
' ( &
,
E is the energy of the n > , shell &recall that for a hydrogen atom
' ( &
,
' ( &
, ! "
E E
' and the
perturbation matri$ element BiRjCis assigned to a parameter v
i!e! z
! z " e( , ,
&+F'
that is proportional to the electric field (! H is Mbloc#-diagonal<) the bloc#s being &, ,') &+ +'
and &+ +'! The energy eigenvalues are obtained in the standard way by setting the determinant
of each bloc# eual to 1ero*
E E
E E
E E v
v E E

' ( &
,
' ( &
,
' ( &
,
' ( &
,
( ( (
( ( (
( (
( (
& E E
' ( &
,
'
,
E E v
v E E

' ( &
,
' ( &
,

>

(
i!e! & E E
' ( &
,
'
,
P& E E
' ( &
,
'
,
N v
,
Q > (
So the four energy eigenvalues are E >
' ( &
,
E )
' ( &
,
E )
' ( &
,
E . v)
' ( &
,
E v! The bloc# diagonal
form of the energy matri$ tells us immediately that two of the eigenvalues are 1ero! In other
words) of the 3 degenerate states ,") ,!
++
) ,!
(
) ,!
+
two of them &,!
++
and ,!
+
' are unaffected by
the electric field and so remain doubly degenerate! The degeneracy of the two remaining levels
is removed as the ," and ,!
(
states combine to produce two new states whose energies are raised
and lowered by an amount v!
+=
+D