L
Tl~)·(g)Tg
Iti·»)
gEG
symmetry
and
the
quantum
mechanical
perturbation
theory;
lilting
of
degeneracy
24.6
IRREDUCIBLE BASIS FUNCTIONS
697
which indicates thatthe inner prodnct on the LHS is independent
of
i,
24.6.2.
Example.
The quantum-mechanical perturhation theory starts with a known
Hamiltonian
Howitheigenvalues Ej andthecorresponding eigenstatesIEj}. Subsequently,
a (small)
perturbing
"potential"
Vis addedto the Hamiltonian, andthe eigenvaluesand
eigenstates of the new
Hamiltonian
H = Ho + V are
sought.
One can
draw
important
conclusions
about
the
eigenvalues
and
eigenstates
of thetotal
Hamiltonian
by
symmetry
arguments.
Supposethesymmetry groupof
HO
is G, andthatof His H, whichhas tohea subgroup
of G. In most cases,theeigenspaces of
HO
are
irreducible
carrier
spacesof G, i.e.,
their
basisvectorstransform according totherowsof irreducible
representations
of G.
If
H is a
propersuhgroupof G, thenthe eigenspacesof Howill splitaccordingto Equation(24.31).
We say thatsome of thedegeneracy is lifted because
of
the
perturbation
V.The
nature
of
the split,
i.e., the
number
andthe dimensionality of the vectorspaces into whicha given
eigenspacesplits,canbeobtainedhy the charactersof G andH andEquation(24.32).The
originaleigenspaces are
represented
on an energy diagram with a line
corresponding
to
eacheigenspace.Thesplitof theeigenspaceinto knew subspaces is thenindicated by the
branching
of theoldline intoknew lines.
To the lowest approximation-first-order
perturbation
theory-the
magnitude
of the
split,i.e., the difference between the eigenvaluesof
HO
andthose of H,is given by [see
Equation (21.57)] the expectationvalue
(oPi·)
IV
loP;·»),
where
loPi·»)
helongs to the ith
row of the
«th irreducihlerepresentation, and
loP]"»)
to its
jth
row (i #
j).
Only if this
expectation valueis
nonzero
will a split
occur.
This, in turn,
depends
on the
symmetry
of
V:
If
V is at least as
symmetric
as
Ho
(corresponding to G = H), then
(¢ja)
IV
ItP)a)}
=0,
andno splitting occurs
(Problem
24.17). If, on the otherhand,V is less
symmetric
than
Ho (corresponding to H c G), then V
loP;·»)
will not belong to the
jth
row of the
cth
irreducIble representation, and in general,
(oPi·)
IV
loP;·»)
#
O.
III
We
had
decomposed the carrier space V
of
a representation into invatiant
irreducible subspaces
WC.).
The
argumentabove shows that
each
WC.) has a basis
consisting
of
the "rows"
of
the irreducible representations. Correspondingto such
a basis, there is a set
of
projection operators
pl·)
with the property L.,i
pla)
= 1
(Chapter 4).
Our
aim is to find an expression for these operators, which have the
defining property
pl·)
Iti
a»)
=
Iti·»).
We start with Eqnation (24.37), multiply
both sides
of
it by
T/~).
(g),
sum over g E G,
and
use Equation (24.8) to obtain
n.
= L
Itya»)
L
T/~)·(g)Tj~a)(g)
j=l
geG
IGI
~
I
(a»)
IGI
I
(.»)
= -
LJ
t
j
8tj8
m
i
8
.p
=-
t
1
8
m
i
8
.p.
n
a
j=l
n
a
Let
fJ
= 01, m = I = i,
and
multiply both sides by n
a
/ 1GI.Then this equation
becomes