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MP364 Ch5
MP364 Ch5
Ĥ = Ĥ0 + W (5.1)
of the time-independent Hamiltonian Ĥ0, whose eigenvalues and eigenvectors are
known and which captures the essential physics, by an additional term
W = λŴ (5.2)
λ 1 (5.3)
We assume that the eigenvalues and eigenstates of Ĥ0 are known and that the un-
perturbed energies form a discrete spectrum E 0p with eigenvectors |ϕipi (where the
index i refers to degeneracy):
where
0
hϕip|ϕip0 i = δ pp0 δii0 (5.5)
XX
|ϕipihϕip| = 1̂ (5.6)
p i
1st order:
Ĥ0 − ε0 |1i + Ŵ − ε1 |0i = 0 (5.12)
2nd order
Ĥ0 − ε0 |2i + Ŵ − ε1 |1i − ε2|0i = 0 (5.13)
q-th order
Ĥ0 − ε0 |qi + Ŵ − ε1 |q − 1i − ε2|q − 2i . . . − εq|0i = 0 (5.14)
We shall write |ψ(λ)i to be normalized and its phase will be chosen s.t. h0|ψ(λ)i ∈ R.
For 0th order we have
h0|0i = 1 (5.15)
λ [h1|0i + h0|1i] = 0
⇒ h0|1i = h1|0i = 0 (5.18)
For the 2nd order we get
1
⇒ h0|2i = h2|0i = − h1|1i (5.20)
2
We will try to answer how a nondegenerate eigenvalue and eigenvector of the unper-
turbed Hamiltonian Ĥ0
ε0 = En0
|0i = |φni
are modified by introducing the perturbation W .
We will be seeking the eigenvalue En(λ) of the full Hamiltonian Ĥ(λ) which when
λ → 0 approaches En0 of Ĥ0.
We will assume that λ is small enough for this eigenvalue to remain non-degenerate.
1. First-order corrections
a. ENERGY CORRECTION
Taking the 1st order equation we found above, and projecting onto |ϕni gives
hϕn| Ĥ0 − ε0 |1i + hϕn| Ŵ − ε1 |0i = 0 (5.22)
and since |ϕni = |0i is the eigenvector of Ĥ0 with the eigenvalue ε0 = En0, we obtain
the first order correction to the energy
ε1 = hϕn|Ŵ|0i = hϕn|Ŵ|ϕni (5.23)
and the 1st order perturbative expression for the energy eigenvalue of the perturbed
system in the form (recall, W = λŴ )
To find the first-order correction to the eigenvector, we must project the first-order
n o
i
equation above onto all the vectors of the |ϕ pi basis other than |ϕni
hϕip| Ĥ0 − En0 |1i + hϕip| Ŵ − ε1 |ϕni = 0 (p , n) (5.24)
Since the eigenvectors of Ĥ0 associated with different eigenvalues are orthogonal
ε1hϕip|ϕni = 0 and hϕip|Ĥ0 = hϕip|E 0p, we get
E 0p − En0 hϕip|1i + hϕip|Ŵ|ϕni = 0 (5.25)
and
1
hϕip|1i = hϕ
0 p
i |Ŵ|ϕ i
n (p , n) (5.26)
En0 − E p
and, since hϕn|1i = h0|1i = 0, the first order correction to the eigenvector can be
written as
X X hϕip|Ŵ|ϕni
|1i = |ϕ ii (5.27)
p
p,n i En0 − E 0p
The expression for the eigenvector of the perturbed Hamiltonian to the first-order is
thus
X X hϕip|W|ϕni
|ψn(λ)i = |ϕni + |ϕ i i + O λ2 (5.28)
p
p,n i En0 − E 0p
The perturbation W mixes the state |φni with the other eigenstates of Ĥ0.
2. Second-order corrections
a. ENERGY CORRECTION
We proceed in a way similar to the previous case. We project the 2nd order equation
obtained above onto |ϕni
hϕn| Ĥ0 − En0 |2i + hϕn| Ŵ − ε1 |1i − ε2hϕn|ϕni = 0 (5.29)
Since |ϕni = |0i is the eigenvector of Ĥ0 with the eigenvalue ε0 = En0, the first term is
zero and the second order correction becomes
ε2 = hϕn|Ŵ|1i (5.30)
With the expression for |1i obtained above we can write the second order correction
to the energy eigenvalue as
X X hϕip|Ŵ|ϕni 2
ε2 = 0 − E0
(5.31)
p,n i E n p
The 2nd order expression for the energy eigenvalue of the perturbed system be-
comes
X X hϕip|W|ϕni 2
En(λ) = En0 + hϕn|W|ϕni + + O(λ3) (5.32)
p,n i En0 − E 0p
b. EIGENVECTOR CORRECTION
onto the set of basis vectors |φipi different from |φni and by using the condition
1
h0|2i = h2|0i = − h1|1i (5.34)
2
c. UPPER LIMIT OF ε2
En0 − E 0p ≥ ∆E (5.36)
then an upper limit for the absolute value of 2 is
1 XX i 2
|ε2| ≤ hϕ p |Ŵ|ϕ n i (5.37)
∆E p,n
i
1 XX i 2
|ε2| ≤ hϕ p|Ŵ|ϕni (5.38)
∆E p,n
i
1 X X
= hϕn|Ŵ|ϕipihϕip|Ŵ|ϕni (5.39)
∆E p,n
i
1 X X
i i
= hϕn|Ŵ |ϕ pihϕ p| Ŵ|ϕni (5.40)
∆E p,n i
An upper limit for the 2nd order term in En(λ) = 0 + λ1 + λ22 + . . . is then
1
λ2ε2 ≤ (∆W)2 (5.44)
∆E
This indicates the order of magnitude of the error committed by taking only the 1st
order correction into account.
C. PERTURBATION OF A DEGENERATE STATE
Assume that the level En0 to be gn-fold degenerate, and E0n be the corresponding
gn-fold dimensional eigenspace of Ĥ0.
ε0 = En0 (5.45)
is not sufficient to determine |0i since the equation Ĥ0|0i = 0|0ican be satisfied by
any linear combination of vectors in E0n.
To determine |0i and 1 we project the 1st order equation
Ĥ0 − ε0 |1i + Ŵ − ε1 |0i = 0 (5.46)
To calculate the eigenvalues (to the 1st order) and the eigenstates (to the 0th or-
der) of the Hamiltonian corresponding to a degenerate unperturbed state En0, we
have to diagonalize the matrix W (n), which represents the perturbation Ŵ inside the
eigenspace E0n associated with the eigenvalue En0.
The first order effect of the perturbation is given by the various roots of the charac-
j (1)
teristic equation of W (n), 1( j = 1, 2, . . . , fn ).
Since W (n) is self-adjoint, its eigenvalues are real numbers and their degrees of
degeneracy sum to gn.
Each eigenvalue introduces a different energy correction, i.e. under W = λŴ , the
(1)
degenerate levels split to the 1st order into fn distinct sublevels
j (1)
En, j(λ) = En0 + λε1 j = 1, 2, . . . , fn ≤ gn (5.53)
j
We shall now choose an eigenvalue 1 of W (n):
and is non-degenerate;