PHAS3226: Quantum Mechanics Dirac Notation Overview

PHAS3226 Dirac Notation Overview

1 Operating on bras and kets

We define the action of an operator in Dirac notation as:
Â|φi = |χi (1)
If φ is an eigenvector of Â, then we find:
Â|φi = λ|φi (2)
We can contract this equation with the corresponding bra to find λ:
hφ|Â|φi = λhφ|φi = λ, (3)
where we’ve assumed that |φi is normalised, i.e. hφ|φi = 1.
Now a bra is just the complex conjugate of a ket, so we should be able to act on a bra with an operator just as we can
act on a ket (and this is one of the more elegant aspects of Dirac notation). Consider Eq. (1). The left-hand side, Â|φi, is
a ket (in fact people sometimes write this as |Âφi). If we take the complex conjugate of the whole of Eq. (1), then we will
find:
 ∗
Â|φi = |χi∗ (4)
hφ|† = hχ| (5)
†
Why do we say that the complex conjugate of Â|φi is hφ|Â ? This comes from the definition of the Hermitian conjugate
of an operator:
hφ|Â|χi∗ = hχ|† |φi (6)
(Note that just as people write |Âφi, they also write hÂφ| = hφ|† . When the operator is inside the bra, it appears as the
operator, but if it is taken outside the bra then it must be the Hermitian conjugate; you might find this easier to understand
if you think about Eq. (1) and Eq. (5) and how they relate. As we have seen, you must be very careful with complex and
Hermitian conjugates !)
Now consider the eigenvalue equation, Eq. (2) above, and take the complex conjugate of both sides. We see:
 ∗
∗
Â|φi = (λ|φi) (7)
hφ|† = λ∗ hφ| (8)
Now perform the same operation on Eq. (3):
hφ|Â|φi∗ = λ∗ (9)
† ∗
hφ|Â |φi = λ (10)
So from this we can write:
† |φi = λ∗ |φi (11)
 ∗
∗
† |φi = (λ∗ |φi) (12)
⇒ hφ|Â = λhφ| (13)
This shows how an operator acts on a bra as well as a ket.

2 An example of the application of Dirac notation

As an example of how Dirac notation and matrix mechanics is used, I will describe some of the techniques used in my
research. Please note that I don’t have time or space to describe this in detail, and there will be some points which I will
ask you to accept (if you are interested, I can point you at further reading).
I use computer programs to solve the Schrödinger equation for groups of atoms, either molecules or solids, or some-
times both. We assume that the ions are classical. The Hamiltonian is quite easy to write down:
X 1
Ĥ = − ∇2i + V̂eI + V̂ee (14)
i
2
XX ZI
V̂eI = (15)
i
|ri − RI |
I
XX 1
V̂ee = (16)
j>i i
|r i − rj |

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PHAS3226: Quantum Mechanics Dirac Notation Overview

where the sum over I is a sum over ions and the sums over i or j are sums over electrons; I’m working in atomic units
(h̄ = c = 0 = me = 1). Notice that the Hamiltonian splits into three parts: kinetic, electron-ion and electron-electron.
To solve this problem, we will make a number of approximations, and then introduce a basis set. The proper solution
of the problem would involve a many-body wavefunction, |Ψi, which was a function of all the positions of all the electrons
(we will look at this type of problem at the end of the course). This cannot be solved analytically, and even approximate
solutions are ferociously complicated.
It is possible to show that, if we can work with a slightly different electron-electron potential (V̂ee ), we can work with
single electron wavefunctions, |ψn i, where there are n electrons in the system. If we have an isolated atom, then we know
how to solve this to a reasonable degree of accuracy (and you saw how to do it for hydrogen last year). One basis set
used for solving problems involving molecules and solids is atomic orbitals: solutions of the Schrödinger equation for
isolated atoms. For now, we will only worry about the valence electrons - that is the outermost electrons (e.g. the 2s and
2p electrons for carbon or the 3s and 3p electrons for silicon).
Then we might write the basis functions as |Iαi where I indicates the ion that we’re dealing with and α indicates
which basis function on that ion we’re considering—atoms will have several (e.g. one s function and three p functions for
carbon or silicon). We would then write:
X
|ψn i = cnIα |Iαi (17)
Iα

Ĥ|ψn i = n |ψn i (18)

and we want to find the values of n , which are the eigenvalues, and possibly the coefficients of the eigenvectors. We will
turn the Schrödinger equation into a matrix equation by expanding out |ψn i and multiplying by hJβ| on the left:

Ĥ|ψn i = n |ψn i (19)

X X
Ĥ cnIα |Iαi= n cnIα |Iαi (20)
Iα Iα
X X
hJβ|Ĥ cnIα |Iαi = n hJβ| cnIα |Iαi (21)
Iα Iα
X X
cnIα hJβ|Ĥ|Iαi = n cnIα hJβ|Iαi (22)
Iα Iα
X
HJβIα cnIα = n cnJβ (23)
Iα

where I’ve assumed that hJβ|Iαi = δJβIα . We’ve seen something like this before: we have reduced the problem to a
matrix problem.
Why would we do this ? There are many automated procedures and libraries which will allow you to find the eigen-
values and eigenvectors for a matrix. So once we have HJβIα , we can pass this to the solver (say in Matlab, Mathematica,
or by linking to a library like Lapack).
Once we have the eigenvalues and the eigenvectors, we can do a number of things. We can calculate the total energy
of the system, and the forces on the ions. This allows us to look at and predict the structure of molecules, surfaces and
solids, and compare the stability of different structures. We can calculate the charge density and predict the spectra of
molecules and solids. There is a huge amount of work in this area, with tens of thousands of papers published each year.
How do we build the Hamiltonian matrix ? We could use position representation, and perform integrals like this:
Z " #
1 2 X ZK
HJβIα = drφJβ (r − RJ ) − ∇ + + Vee (r) φIα (r − RI ) (24)
2 |r − RK |
K

with the basis functions defined roughly as φIα (r) = Yml (θ, ϕ)Rl (|r|). There are approaches that do this, for instance the
Gaussian code (whose creator, John Pople, shared the Nobel Prize in Chemistry for work in this area).
Another approach, known as tight binding, is to fit the Hamiltonian matrix elements. In this approach, we use data
from experiment and other modelling to fit values of different matrix elements for structures with high symmetry and
equilibrium bond lengths. We can also fit the change of matrix elements with the distance between ions to a power law.
Using this approach, simple, qualitative calculations can be made very quickly.

3 Some exercises you might try

Here are some exercises you might try to improve your grasp of Dirac notation. Except for the last question, the answers
are to be found in the notes, but you should try to do them without the notes !

• Show that the sum of two eigenvectors of an operator is also an eigenvector (|ψi = c1 |ψ1 i + c2 |ψ2 i)

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PHAS3226: Quantum Mechanics Dirac Notation Overview

P
• Derive the expansion coefficient for a wavevector (|ψi = n cn |ni)

• Show that the eigenvalues of a Hermitian operator are real

• Show that the eigenvectors corresponding to different eigenvalues are orthogonal

• Use closure to derive thePexpansion coefficient for a wavevector, if you didn’t above (i.e. use the identity operator
in a complete basis Iˆ = n |nihn| and write |ψi = I|ψi)
ˆ

• Express the matrix elements of an operator  in a basis

• Convince yourself that you understand why the similarity transform, Smn = hχm |ψn i can be used when changing
from a representation in terms of |ψn i to a representation in terms of |χm i

• Assume that a hydrogen atom only has one atomic orbital (the 1s function). Then consider how you might perform
a tight binding calculation on H2 : let |Ĥ|ii =  and hi|Ĥ|ji = hj|Ĥ|ii = h. You should be able to diagonalise this,
and find the two eigenvalues. What is the separation between them ? How does it change as h becomes small ? As
electrons have spin up and spin down, we would only fill the lowest eigenstate. What is the total energy of H2 , and
how does it compare to two hydrogen atoms ?

4 Two worked examples

Here are two example problems from previous problem sheets, and their answers, using Dirac Notation.

4.1 Questions
1. The observable A is represented by operator Â. The eigenvectors of  are |φ1 i and |φ2 i which are orthonormal.
The corresponding eigenvalues are +1 and −1 respectively. The system is prepared in a state |ψi given by
4
|ψi = |φ1 i + c|φ2 i.
10
(a) If the state |ψi is normalized what is the value of |c|? [2]
(b) Calculate the numerical value of the expectation value of  in the state |ψi. [4]
(c) With the system in the state |ψi a measurement of observable A is made. What is the probability of obtaining
the eigenvalue −1? [2]
(d) Immediately after the measurement is made, with the result −1, what is now the expectation value of Â?
Explain your answer briefly. [2]
2. An harmonic oscillator is in the state |ψi = √16 |0i + √26 |1i + √16 |2i. Evaluate in this state |ψi the expectation value
of x̂. (N.B. If you want to understand the value of Dirac notation in this situation, try to evaluate the expectation
value in this state using position representation and the explicit form of the QHO eigenstates !).

4.2 Answers
√
16 2 84
1. (a) Normalization requires 1 = 100 + |c| , so c = 10 ' 0.9165.
(b) The expectation values of  in state |ψi is
D E 4  
4

∗
ψ|Â|ψ = hφ1 | + c hφ2 | Â |φ1 i + c|φ2 i (25)
10 10

Using the eigenvalue equations Â|φ1 i = +|φ1 i and Â|φ2 i = −|φ2 i

  
D E 4 ∗ 4
ψ|Â|ψ = hφ1 | + c hφ2 | |φ1 i − c|φ2 i (26)
10 10
16 2 16 84 68
= − |c| = − =− (27)
100 100 100 100
P 2 16 84
Alternatively, and far quicker, can calculate the expectation value from n |cn | an i.e. 100 (1) + 100 (−1) =
68
− 100 .
84
(c) The probability is the modulus squared of the coefficient of the state |φ2 i, i.e.100 .

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PHAS3226: Quantum Mechanics Dirac Notation Overview

(d) Immediately after the measurement the system is in state |φ2 i. Hence the expectation value for  is −1.
h̄

1/2
2. Since x̂ = 2mω (â+ + â− ) then its expectation value in the state |ψi = √16 |0i + √26 |1i + √16 |2i is given by
  1/2  
1 2 1 h̄ 1 2 1
hψ|x̂|ψi = √ h0| + √ h1| + √ h2| (â+ + â− ) √ |0i + √ |1i + √ |2i . (28)
6 6 6 2mω 6 6 6
√ √
Using the actions of a+ and a− on states |ni, i.e. â+ |ni = n + 1|n + 1i and â− |ni = n|n − 1i and the
orthonormality of the basis states, hn|mi = δnm we get
 1/2   √ √ √ !
h̄ 1 2 1 2 1+ 2 2 2 3
hψ|x̂|ψi = √ h0| + √ h1| + √ h2| √ |0i + √ |1i + √ |2i + √ |3i ,
2mω 6 6 6 6 6 6 6
 1/2  √ √ √ √ 
h̄ 1 2h0|0i
= √ + (1 + √ 2)h0|1i + 2 2h0|2i + 3h0|3i
√ + 4h1|0i
√+ 2(1 + √2)h1|1i ,
2mω 6 +4 2h1|2i + 2 3h1|3i + 2h2|0i + (1 + 2)h2|1i + 2 2h2|2i + 3h2|3i
1/2 √  1/2
√ √  2+2 2

h̄ 1 h̄
= 2 + 2(1 + 2) + 2 2 = .
2mω 6 3 2mω