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Matrix Mechanics
We now turn to the a pragmatic aspect of QM: given a particular
problem, how can we translate the Dirac notation into a form that
might be interpretable by a computer? As hinted at previously, we do
this by mapping Dirac notation onto a complex vector space. The
operations in Hilbert space then reduce to linear algebra that can
easily be done on a computer. This formalism is completely
equivalent to the Dirac notation we’ve already covered; in different
contexts, one will prove more useful than the other.
1. States can be represented by vectors
First, we will begin with an arbitrary complete orthonormal basis of
states {φi }. Then, we know that we can write any other state as:
ψ = c1 φ1 +
c
2 φ2 +
c
3 φ3 + ... = ƒ
ci φi
i
How are these coefficient determined? Here, we follow a common
trick and take the inner product with the jth state:
( ) ( ) ( )
φ j ψ = φ j ƒ
ci φi = ƒ
ci φ j φi = ƒ
ciδ ij
i i i
Since the Kronecker delta is only non-zero when i=j, the sum
collapses to one term:
φj ψ = cj
The simple conclusion of these equations is that knowing the
coefficients is equivalent to knowing the wavefunction. If we know
ψ , we can determine the coefficients through the second relation.
Vice versa, If we know the coefficients, we can reconstruct ψ by
performing the sum ƒ ci φi .
Thus, if we fix this arbitrary basis, we
i
can throw away all the basis state and just keep track of the
coefficients of the ket state:
≈ c1 ’
Δ ÷
ψ → ΔΔ 2 ÷÷
c
c
ΔΔ 3 ÷÷
« ... ◊φ
In harmony with the intuitive arguments made previously, here we
associate the ket states with column vectors. Notice the small
subscript “ φ ”, which reminds us that this vector of coefficients
represents ψ in the {φi } basis. If we were really careful, we would
keep this subscript at all times; however, in practice we will typically
know what basis we are working in, and the subscript will be dropped.
«
i ◊ i
ψ ψ ' =
Δ ƒ φi ci* ÷ΔΔ ƒ
c 'j φ j ÷÷ = ƒ
ci*c 'j φi φ j = ƒ
ci*c 'jδ ij = ƒ
ci*ci'
«
i ◊« j ◊ ij ij i
≈
c1 ’
Δ ÷
(c1* c2* c3* ...)φ ⋅ ΔΔ c2 ÷÷ = ƒ
ci*ci'
c
ΔΔ 3 ÷÷
«
... ◊φ
So, the two ways of writing the inner product give identical results,
and overlaps between the vectors have the same quantitative (and
qualitative) meaning as their bra-ket counterparts.
2. Operators Become Matrices
In order to complete our transition to linear algebra we need to
determine how operators act on the coefficient vectors described in
the previous section. Before we do this, we need to consider the
operator:
Ô = ƒ φi φi
i
Acting this operator on an arbitrary state:
Ô ψ = ƒ φi φi ψ
i
Thus, Ô acting on any state gives the same state back. The operator
that accomplishes this is the identity operator, 1̂ , and so we write:
1̂ = ƒ φi φi
i
and say that this is a resolution of the identity.
1ˆ = ƒ φi φi 1ˆ = ƒ φ j φ j
i j
Ω ƒ ψ φi φi  φ j φ j ψ '
ij
Ω ƒ ci* φi  φ j c 'j
ij
Ω ƒ aα χ β ϕ α = bβ
α
This leads to the definition of the Transformation matrix:
≈
χ1 ϕ1 χ1 ϕ 2 χ1 ϕ 3 ...
’
Δ ÷
Δ χ 2 ϕ1 χ2 ϕ2 ... ... ÷
T≡Δ ÷
χ ϕ ... ...
ΔΔ
3 1 ÷÷
«
... ... ◊
The columns of this matrix are the coefficients of the “new” basis
states ( { χ α }) in terms of “old” ones ( {ϕα }) and it allows us to
transform from one basis to another using simple matrix algebra:
b = Ta
Δ ÷
Δ ϕ 2 Ĥ ϕ1 ϕ 2 Ĥ ϕ 2 ... ÷
Δ ϕ Ĥ ϕ ... ÷ ≡ HA
Δ 3 1 ÷
Δ
... ÷
«
◊
÷
◊
«
0 ... ... ...
÷
Ω
f (A ) =
TΔ 1 + f '
(0 )A A + A AA A + A A A A A A +
...
÷T
†
« 2! 3! ◊
Ω
f (A ) = Tf (A A )T †
Δ ÷ Δ ÷
Δ0 e2 0 0÷ Δ 0 f (e2 ) 0 0÷
f (A A ) = f Δ =
0 0 e3 0÷ Δ 0 0 f (e3 ) 0 ÷
ΔΔ
÷÷ ΔΔ ÷
«
0 0 0 ...◊
«
0 0 0 ...÷
(
= − 12 n + 2 n + 1δ m ,n +2 − (2n + 1)δ m ,n + n − 1 nδ m ,n−2 )
while the matrix elements of qˆ are:
(
m qˆ n = 12 m (aˆ † +
aˆ ) n = 12 n + 1δ
m ,n +1 + nδ m ,n−1 )
Δ ÷ Δ ÷
Δ 1 0 2 ... ÷ Δ 0 3 0 − 6 ÷
Q ≡ 12 Δ P 2 ≡ 12 Δ
0 2 0 3 ÷ − 2 0 5 0 ÷
Δ ÷ Δ ÷
Δ ... ... ÷ Δ ... −
÷
«
3 ... ◊ « 6 0 ... ◊
Thus far, we have just been applying the rules of matrix mechanics.
pˆ 2
Now, if our Hamiltonian takes the standard form H = ˆ + V (qˆ ) then
2m
P2
we can easily translate this into matrix mechanics: H = + V (Q ) .
2m
The only tricky part is how we evaluate V (Q ) ; in DVR we follow the
prescription above and diagonalize Q , evaluate V (Q ) in the
eigenbasis and then transform back to the harmonic oscillator basis:
V (Q) = TV (Q q )T† . As mentioned above, evaluating V (Q q ) is simple; it
is just a diagonal matrix with diagonal elements given by the function
V evaluated at the eigenvalues of Q .
pˆ 2
Therefore, we know how to represent H = ˆ + V (qˆ ) as a matrix in
2m
the harmonic oscillator basis. We have made no approximations
(yet). However, we have a bit of a problem, because the matrices Q
and P 2 are infinite-dimensional. This is a bit of a problem on a (finite)
computer. The key approximation we make is that of a truncated
basis: we select some large but finite number of basis functions, N .
For example, we might choose the N lowest energy states of the
harmonic oscillator if we are interested in the low energy states of
pˆ 2
Hˆ = + V (qˆ ) . Once we have selected our truncated basis, we
2m
perform the entire problem as if these functions form a complete
basis. As a result, Q and P 2 go from being infinite dimensional
matrices to being N × N matrices that we can store on a computer.
The key observation is that, as I make N larger and larger, my
truncated basis becomes closer to the complete basis and all the
results I compute in the truncated basis (e.g. energy eigenvalues,
expectation values, etc.) must approach the corresponding complete
basis results. Since one can easily deal with N up to several
thousand on a computer, this makes it possible to obtain very precise
answers for one-dimensional problems.
P2
5) Construct H = + V (Q ) and compute whatever you need (e.g.
2m
eigenvalues, eigenstates, average values) using matrix
mechanics.
C. Variational method
One important point is that the DVR representation is not unique.
The ambiguity comes because we have chosen to compute the
matrix representation of certain “basic” operators ( pˆ 2 and qˆ ) directly,
while other operators (V (qˆ ) ) have been represented as functions of
the “basic” matrices. Toe see where the ambiguity arises, let’s
pretend we’ve chosen a very small basis: N =3. There are two ways
we could compute P 2 . The first is to compute its matrix elements
directly:
≈ 1 0 −
2 ’
Δ ÷
P 2 ≡ 12 Δ 0 3 0
÷
Δ
−
2 0 5 ÷
«
◊
Δ ÷ Δ ÷ Δ ÷
P ⋅ P =
12 Δ − i 0 i 2 ÷Δ − i 0
i 2 ÷ = 12 Δ 0 3 0 ÷
Δ 0 −i 2
«
0 ÷◊Δ« 0 − i 2 0 ÷◊
Δ
«
2 0 2 ÷
And the results are clearly different. Note that if we had chosen a
larger N , these two routes would have given (essentially) the same
answer. However, it is clear that, for finite N the way we choose to
represent things in terms of matrices matters.
ψT ψT ƒ
α φj ƒ
α φi ƒ
α φj ƒ
α φi
* *
j i j i
j i j i
ƒ
α φj ƒ
α E φi ƒα α i Ei φ j φi
* *
j i i j
= j i
=
ij
�
ij
ƒ
α j φ j ƒ
αi φi ƒα j αi φ j φi
* *
j i ij
ƒα α E
*
i i i
= i
ƒ
α α
*
i i
i
Thus we see that the average energy for any trial state must be
greater than or equal to the ground state energy. This gives us a
clear-cut way to determine the “best” approximation to the ground
state out of a set of trial functions: whichever ψ T has the lowest
average energy is physically the best approximation to the ground
state.
Given the definition of the ket trial state, the bra state is just the
hermitian conjugate:
N
ψ T (c ) = ƒ φ i ci
*
i =1
ƒ φi ci * Hˆ ƒ c j φ j ƒc
*
φi Hˆ φ j c j
ψ T (c *) Hˆ ψ T (c ) i
ET (c, c *) =
i =1 j =1 i , j =1
= =
ψ T (c *) ψ T (c ) N N N
ƒφ
i =1
i ci
*
ƒc
j =1
j φj ƒφ
i , j =1
i φ j ci * c j
N
ƒc φi
Hˆ φ j c j
*
i
i , j =1
= N
ƒc i =1
i
*
ci
ƒ ci φi Hˆ φ j c j ƒ φ k Hˆ φ j c j ƒc φi Hˆ φ j c j
* *
∂ET (c, c *) ∂
i
i , j =1 j =1 i , j =1
0= = = − ck
∂c k ∂c k
* * N N 2
≈ N * ’
ƒc ƒc
* *
i ci i ci Δ ƒ ci c i ÷
i =1 i =1
« i =1 ◊
N
ƒφ
j =1
k Hˆ φ j c j
ET (c, c *)c k
= N
− N
ƒ ci ci
i =1
*
ƒc
i =1
i
*
ci
N N N
∂E (c, c *) ∂
ƒ ci * φi Hˆ φ j c j
i , j =1
ƒ ci * φi Hˆ φk ƒc
i , j =1
i
*
φ i Hˆ φ j c j
0= T = = i =1
−
*
ck
∂c k ∂c k N N
≈ ’
2
ƒc ƒc
* * N
ci ci Δ ƒ ci ci ÷
*
i i
i =1 i =1
« i =1 ◊
N
ƒc φi Hˆ φ k
*
ET (c, c *)c k
i *
= i =1
N
− N
ƒc ƒc
* *
i ci i ci
i =1 i =1
and
N
Ω 0 = ƒ ci φi Hˆ φ k − ET (c, c *)c k .
* *
i =1
In practice, we can apply the variational method the same way DVR
is used: First, we need to choose an appropriate orthonormal basis
{φi }. Second, we need to build the matrix representation of the
Hamiltonian in the HO basis:
p2
H mn ≡ m + V (x ) n
2m
This is usually the most tedious step of the calculation, as it involves
a good deal of algebra deriving the general matrix elements and a
nontrivial amount of computer work to make sure the matrix is built
properly. Finally, we diagonalize the matrix H to obtain the
approximate eigenvalues. As an additional check, we should
increase N and re-run the calculation to see that the result is
converged.