6.

Operator Representation, December 14, 2009

Chapter 6. Operator Representation Theory

Section 6.1. Kets and vectors, operators and matrices 1 The representation of kets. Let us assume that we have dened a complete, orthonormal basis set |a1 , . . . , |an , . . . and | with D. It satises the completeness relation = I
n=1

|an an | +

d | |

(1)

and the orthonormality relations an | am = nm | = ( ) an | = 0 (2) (3) (4)

One of the most frequent uses of the completeness relationship is to write an arbitrary ket | as (see Chapter 3) | = | = I
n=1

|an an | +

d | |

(5)

The scalar products an | and | are complex numbers. Since we have imposed no condition on | , we can represent in this way any ket in the space. One calls the set of all kets | that can be represented by Eq. 5 the linear space spanned by the orthonormal basis set |an , n = 1, 2, . . ., and | , D. Whenever we use a basis set, it is assumed that the kets |an , n = 1, 2, . . ., and | , D are known. By this I mean that we know how to evaluate any expression involving them. Because of this, we can state that Eq. 5 shows that knowing the numbers an | , n = 1, 2, . . ., and | , D, is equivalent to knowing | . Many calculations that aim at obtaining | do so by deriving equations for the numbers an | and | . Once these numbers are known, we use them in Eq. 5 to calculate | . We say of Eq. 5 that it gives | in the basis set { {|ai } i=1 , {| }D }. If the basis set consists of the pure states of an observable A, then we say that Eq 5 gives | in the A-representation (remember that if |an and | are pure states of the observable A then they are the eigenstates of the operator ). The numbers an | and | are called the coordinates of | in A

6. Operator Representation, December 14, 2009

the A-representation or the components of | in the A-representation or the amplitudes of | in the A-representation. The list { { a1 | , a2 | , . . .}, { | }D } (6) is an innite-dimensional vector that represents the ket | . In what follows, I will often use the notation i ai | and | (8) The notation ai | is more complete, because it species the basis set used to represent | , but i is simpler (we use it only when it is clear which basis set is being used). It is worth noting that the symbol = { { a1 | , a2 | , . . .}, { | }D } is ordered. A symbol containing the same numbers but in dierent order represents a dierent ket (in 2 ). In many practical calculations involving bound states, we can neglect the integral over the continuous spectrum in Eq. 5 and take a nite number N of terms in the sum. Then
N

(7)

| =

n=1

|an an |

(9)

and the ket | is represented by the N -dimensional vector = { a1 | , a2 | , . . . , aN | } {1 , 2 , . . . , N } (10)

This is a vector in CN . The kets of the basis set are represented in the space in CN as follows. |a1 is represented by a[1] {1, 0, 0, . . . , 0}, (11) |a2 by a[2] {0, 1, 0, . . . , 0}, (12)

6. Operator Representation, December 14, 2009

and so on, with |aN represented by a[N ] {0, 0, 0, . . . , 1} We obtain Eq. 11 by applying Eq. 9 to | = |a1 , which becomes
N

(13)

|a1 =

n=1

|an an | a1

(14)

The amplitudes of |a1 in this representation are a[1] { a1 | a1 , a2 | a1 , . . . , aN | a1 } = {1, 0, 0, . . . , 0} Eqs. 1213 are obtained similarly. The scalar product of two kets is represented in the space CN by | = =
n=1

(15)

= |I
N

N n=1

| an an | =

n=1

an |

an | (16)

n n

The specic numbers {1 , . . . , N } { a1 | , . . . , aN | } that represent a ket | depend on the basis set {|a1 , . . . , |aN }. Had we chosen a dierent basis set {|b1 , . . . , |bN }, the same ket | would have dierent coordinates, namely, { b1 | , . . . , bN | }. This chameleon-like ability of a ket to appear as dierent vectors in CN is useful in performing computations and in interpreting their results. 2 Operators and matrices. We have used an orthonormal, complete basis to represent kets as vectors in CN . How can we use the completeness relation to represent operators by objects acting on those vectors? : We start with the obvious equality for an operator O =I O I O with the expression given by Eq. 1, to obtain and replace I = O

(17)

n=1 m=1

|an Onm am | +

n=1 D

d |an On | d
D

n=1 D

d | On an | +

d | O |

(18)

6. Operator Representation, December 14, 2009

In this expression | am Onm an | O and | O | O (20) The symbols On and On are dened similarly. The complex numbers Onm , On , On , and O are called the matrix in the basis set { {|an } , {| }D }. If |an elements of the operator O n=1 and | are pure states of an observable A, then we say that Onm , On , in the A-representation. If we On , and O are the matrix elements of O know how to perform calculations with the kets forming the basis set, Eq. 18 implies that knowing these matrix elements is equivalent to knowing how to perform calculations with the operator. 3 Finite-dimensional approximation. It is extremely fortunate that in many practical applications in quantum mechanics, we can dispense with the integral in Eq. 1 and retain only a nite number of terms in the sum, to write N = I |an an | (21)
n=1

(19)

This is an approximation and its accuracy depends on which basis set we use, what quantity we calculate, and how many terms we keep. Here I assume that N has been chosen appropriately and will go on to derive the consequences of this approximation.1 Its great power comes from the fact that it reduces problems in quantum mechanics to problems in linear algebra. I assume that you dont know linear algebra well and I will teach what you need as we go along. All but the most trivial calculations in linear algebra require a computer. I will use Mathematica and you can look up the le linear algebra for quantum mechanics.nb to see how this programming language performs linear-algebra operations.
When examining the eect of collisions or processes that cause the dissociation or the ionization of a molecule, it is impossible to ignore the continuous part (the integral) in the completeness relation, because the nal state of the system has a continuous energy. Such processes are discussed separately. The theory developed here is applicable to the bound states of molecules. Even for these states, neglecting the integral is an approximation (very often a good one).
1

6. Operator Representation, December 14, 2009

With the truncation established above, we can write

N N

| = and = O
N N

n=1

|an an |

n=1

|an n
N

(22)

n=1 m=1

|an

| am am | an | O

n=1 m=1

|an Onm am |

(23)

4 Connecting operators to matrices. Let us now ask how the expression | | O (24) translates into a representation in the space CN generated by the orthonormal basis set {|an }N n=1 . We can represent | as
N N

| = where

n=1

|an an | n an |
N

n=1

n |an

(25)

(26)

| is represented by (use Eq. 23) The expression O | | O

N

=
n=1 m=1 N N

| am am | |an an | O |an Onm m (27)

=
n=1 m=1

Here m am | are the components of | in the basis set |am , (m = | am Onm are the matrix elements of O in that 1, 2, . . . , N ) and an | O basis set. We can easily calculate k ak | from Eq. 27:
N N

k =

ak | = ak |
N N

n=1 m=1

|an Onm m

n=1 m=1 N N

ak | an Onm m
N

=
n=1 m=1

kn Onm m =
m=1

Okm m

(28)

6. Operator Representation, December 14, 2009

| : nd the components m This provides a route for computing | O | am of O ; insert am | of | and the matrix elements Onm an | O them in Eq. 28 and calculate the components n an | of | ; use n in Eq. 25 to calculate | . The result can be used to evaluate any expression containing | . This is one of the most widely used methods for performing computations in quantum mechanics. 5 Matrices in linear algebra. In linear algebra, the matrix elements Onm are thought of as forming one object, called a matrix. In of an operator O by the letter O. Often a what follows, I denote the matrix of an operator O matrix is written as a table
O=

O11 O21 . . .

O12 O22 . . .

ON 1 ON 2

O1N O2N . ... . . ON N

(29)

The matrix elements {Oi1 , Oi2 , . . . , OiN } form the i-th row in the matrix, and{O1i , O2i , . . . , ON i } form the i-th column. Since we can add operators, we can dene addition rules for the corresponding matrices. You can easily show that if A +B C ) are then the matrix elements of the matrix C (representing C Cnm = Anm + Bnm , n, m = 1, 2, . . . , N It is therefore natural to dene the sum of two matrices A and B by

(30)

(31)

A11 A21 . . .

A12 A22 . . .

AN 1 AN 2

A1N A2N . ... . . AN N

+ =

B11 B21 . . .

B12 B22 . . .

BN 1 BN 2 A11 + B11 A21 + B21 . . .

B1N B2N . ... . . BN N

A12 + B12 A22 + B22 . . .

...

A1N + B1N A2N + B2N . . .

AN 1 + BN 1 AN 2 + BN 2 AN N + BN N (32)

6. Operator Representation, December 14, 2009

A are Also, the matrix elements of O Onm = Anm (33) and this denes the rule for multiplying a matrix by a complex number. can act on a ket | to give the ket | = O | . The An operator O representation of this operation by a vector and a matrix is given by Eq. 28. The matrix O acting on the vector = {1 , 2 , . . . , N } gives the vector = {1 , 2 , . . . , N } with components
N

n =
m=1

Onm m

(34)

In matrix theory, this is a denition. In quantum mechanics, we are often required to evaluate expressions of B | . What is the matrix representation of the product the form | = A =A B ? C in the basis set {|an }N are The matrix elements of C n=1 Cnm =
j =1 N

(35)

| am = an | A B | am = an | A I B | am an | C | aj an | A | am = aj | B
N

Anj Bjm
j =1

=A B from those of Thus, the rule for generating the matrix elements of C A and B is
N

Cnm =
j =1

Anj Bjm , n, m = 1, 2, . . . , N

(36)

This denes the product of matrix A with matrix B . Exercise 1 Derive the vector-and-matrix representation (use the orthonormal and complete basis set {|an }N n=1 ) of the following expressions: |x = |y A |x = |x A 1 A U |x = | U =A B B A C (37) (38) (39) (40)

6. Operator Representation, December 14, 2009

Exercise 2 If
N and {|an }N n=1 and {|bn }n=1 are two complete, orthonormal basis sets, can I in the basis {|an }N by using calculate matrix elements of C n=1

A B C

(41)

| am = an | C

| bj an | A

| am ? bj | B

(42)

Exercise 3 You are given x = {0.1, 0.3, 2.2} y = {0.1 + 6.2i, 0.3 + 2.1i, 0.4 + 0.2i} 3.1 2.4 6.3 A= 2.7 1.4 5.6 2.9 3.2 1.5 2.1 0.3 1.4 B = 5.6 1.7 2.6 0.2 0.7 1.6

Calculate (1) y | x ; (2) x | y ; (3) Ax; (4) BA; (5) AB ; (6) BAy ; (7) AB y .

6 A historical note. Quantum mechanics was discovered by Heisenberg during a vacation on an island in the Baltic Sea, where he went to cure an attack of hay fever. In his formulation the state of a harmonic oscillator was described by a vector with an innite number of components. The Hamiltonian of the oscillator was represented as a matrix. The equivalent of the Schr odinger equation (which was not known at that time) was an eigenvalue problem for the Hamiltonian matrix. For a harmonic oscillator this problem is simple and Heisenberg solved it. He showed his results to his supervisor, Max Born, who realized that Heisenberg was doing matrix algebra. At that time, physicists did not know linear algebra but Born did. He had been an assistant to the great mathematician David Hilbert and was well-trained in mathematics. Together with his student Jordan, he generalized Heisenbergs theory and also noted that the key dynamical assumption, central to

6. Operator Representation, December 14, 2009

the theory, was a statement about the commutator of the matrix representing position and that representing momentum. Later Heisenberg, Jordan, and Born wrote a paper that established most of the rules of quantum mechanics, as they appear in the matrix representation. At about the same time, Dirac reformulated Heisenbergs theory in terms of operators, which he called q-numbers. Shortly after that, Schr odinger published a version of quantum mechanics based on a dierential equation. Within one year, he discovered what is now known as the Schr odinger equation, solved it for the hydrogen atom and for the harmonic oscillator, and introduced perturbation theory to deal with the Stark eect and with the eect of time-dependent elds. Physicists adopted Schr odingers theory enthusiastically since they were very good at solving dierential equations and liked the fact that they could draw pictures of the wave function , even though they had no idea what represented. Prior to Heisenbergs work, quantum theory was a collection of somewhat arbitrary improvisations. In less than two years, physicists were presented with three competing theories that gave the same results when used to calculate observables but were completely dierent in their form. Schr odinger showed that by expanding the wave function in an orthonormal, complete basis set, he could derive Heisenbergs theory from his. Later Dirac introduced the bra-and-ket mode of writing the equations and developed what he called the transformation theory, which showed that all these theories are just dierent representations of the same reality. Matrices were introduced in mathematics by Cayley, who was interested in the manner in which the quadratic form
N N

cij xi xj
i=1 j =1

behaves when one changes the variables xi . Matrices appear naturally in the theory of linear systems of algebraic equations of the form
N

cnm xm = yn , n = 1, 2, . . . , N
n=1

(43)

where cnm are known coecients, yn are the known components of a vector, and xm are to be determined. This is often written as Cx = y

6. Operator Representation, December 14, 2009

10

where C is the matrix having the elements cnm and x and y are vectors having the components xn and yn , respectively. Another way of writing Eq. 43 is

Cayley discovered new and useful mathematics while making money as a reluctant, but successful, lawyer. After 13 years of lawyering, he happily quit for a less protable professorship at Cambridge University. He was uent in many languages, knowledgeable of arts and literature, and a vigorous hiker. Section 6.2. Special matrices for special operators We have introduced the adjoint and the inverse of an operator, and pointed out that Hermitian and unitary operators have useful properties. What kind of matrices represent such operators? Does the matrix of a Hermitian operator, for example, have any special properties? In what follows, we examine the properties of a few special matrices. | aj of 7 Diagonal matrices. We have dened the elements Cij = ai | C in the A-representation through the matrix representing an operator C = C

c11 . . .

cN 1

c1N x1 y1 . . . ... . . . . . = . cN N xN yN

i=1 j =1

| aj |ai ai | C

aj |

(44)

through If C is an observable and its pure states are |cn , then we dened C = C
i=1

|cn cn cn |

(45)

Here cn , n = 1, 2, . . ., is the spectrum of C. in the A-representation and Eq. 45 gives C in the CEq. 44 gives C representation. We can rewrite Eq. 45 as = C

m=1 n=1

|cm cm nm cn |

(46)

since nm = 0 if n = m and nm = 1 if n = m. Compare Eq. 46 to the general | cm of C in equation, Eq. 44. You can see that the matrix elements cn | C its own representation are | cm = cm nm Cnm cn | C (47)

6. Operator Representation, December 14, 2009

11

diagonalize the matrix C . We say that the eigenvectors of C In any representation using an orthonormal basis set, the matrix elements of the unit operator are | j = i | j = ij i | I The unit operator is represented by the matrix (usually denoted by I )

A matrix having elements of this is c1 0 0 c2 0 0 . . . . . . 0

form is called diagonal, because its table

0 0 0 0 c3 0 . . ... . . . . 0 0 cN

(48)

(49)

0 0 1 . ... . . 0 0 0 1 0 0 . . . 0 1 0 . . .

0 0 0 . . . 1

(50)

in which the diagonal elements are all equal to 1 and the o-diagonal elements are all equal to 0. 8 Adjoint matrices. For each operator = A
n

|an an an |

(51)

we have dened the adjoint operator by = A

n

|an a n an |

(52)

We have shown that for any two kets | and | , = A | |A (53) in an arbitrary complete basis The matrix elements (A )nm of the operator A set {|cn } satisfy cm = Ac n | cm = cm | A | cn (A )nm cn | A

= A mn

(54)

6. Operator Representation, December 14, 2009

12

has the matrix elements Anm (in some representation) Thus, if the operator A has the matrix elements A (in the same representation). For then A mn in a three-dimensional representation is example, if the matrix of A

1.2 1.7 3.1

2.4 + i2.1 6.5 3.5 2.1 i3.2 = matrix of A 1.5 + i4.3 3.7

(55)

in the same representation is then the matrix of A 1.2 1.7 3.1 3.5 1.5 i4.3 2.4 i2.1 = matrix of A 6.5 2.1 + i3.2 3.7 (56)

Eq. 54 tells us that to obtain the adjoint matrix A from A, we perform two operations. (1) We create the transpose matrix AT whose elements are (AT )ij = Aji . This amounts to taking the rst row of A and making it the rst column of AT , taking the second row of A and making it the second column of AT , etc. (2) We obtain A by (complex-)conjugating each element of AT . given by 9 Inverse matrices. In Chapter 4, I dened for an operator A = A the inverse 1 A
n=1

|an an an |, 1 an | an

(57)

n=1

|an

(58)

I showed that this denition is equivalent to =A A 1 = I 1 A A (59)

and also cautioned you that some operators do not have an inverse. The matrix representation of Eq. 59 is obtained as follows. Let {|cn }N n=1 be an orthonormal, complete basis set. From Eq. 59 we have | cm = cn | A 1 A | cm = cn | I
N j =1

1 | cj cn | A

| cm cj | A

(60)

6. Operator Representation, December 14, 2009

13

However, | cm = cn | cm = nm cn | I Combining Eqs. 60 and 61 gives

N

(61)

(A1 )nj Ajm = nm

j =1

(62)

A 1 = I becomes Similarly A
N

Anj (A1 )jm = nm

j =1

(63)

These equations dene the matrix elements (A1 )ij of the inverse matrix A1 . Unfortunately there are no easy-to-use rules for calculating the inverse of an operator (or that of a matrix) by hand. Such a calculation is equivalent to solving the equation |x = |y A (64) 1 on Eq. 64 gives for |x . Indeed, acting with A 1 A |x = A 1 |y A 1 A =I , we have Since A 1 |y |x = A (65) (66)

|x = |y can easily be transcribed to its matrix equivalent by The equation A N using the basis set {|cn }N n=1 |cn cn |. n=1 and the completeness relation I = Indeed, from Eq. 64, | x = cn | y cn | A (67) and |x = cn | A
N m=1

| cm cm | x cn | A

N m=1

Anm cm | x

(68)

|x = |y Combining Eqs. 67 and 68 tells us that the matrix equivalent of A is the system of N linear equations
N m=1

Anm cm | x = cn | y , n = 1, . . . , N

(69)

6. Operator Representation, December 14, 2009

14

If we use the notation cn | x xn and cn | y yn , then Eq. 69 is

Any numerical or analytical procedure that solves this equation and gives the result in the form
N

A11 . . .

AN 1

A1N x1 . . ... . . . . = AN N xN

yN

y1 . . .

(70)

xi =
j =1

Bij yj

(71)

gives the inverse of the matrix Aij (the inverse of A being the matrix with elements Bij ). It is important to understand that not every system of linear equations has a solution. This is equivalent to saying that not every matrix has an inverse. There is a theorem in linear algebra that states that a matrix A has an inverse if and only if its determinant is non-zero: A1 exists if and only if det A = 0 Recall that 1 = A
i

(72) (73)

|ai

1 ai | ai

1 is not dened if the operator A has a zero in its spectrum The inverse A (i.e. if one or more ai is equal to 0). Since the spectrum is obtained by solving the eigenvalue problem |ai = ai |ai (74) A does not have an inverse if one of its eigenvalues is zero. we can say that A ? How is this connected to the determinant of the matrix representing A in the A-representation is diagonal: The matrix of A | aj = ai ij ai | A The determinant of a diagonal matrix is
det

(75)

m1 0 0 0 m2 0 0 0 m3 . . . . . . . . . 0 0 0

...

0 0 0 . . .

mN

= m1 m2 mN

(76)

6. Operator Representation, December 14, 2009

15

If one eigenvalue ai is zero then the determinant of the matrix is zero: either (or A) does not have an inverse. condition tells us that A There is a weakness in this discussion. It shows that the determinant of has a zero eigenvalue. However, if I A in the A-representation is zero if A want to solve |x = |y , A (77) I can use the B-representation to turn Eq. 77 into
N j =1

| bj bi | A

bj | x = bi | y , i = 1, . . . N

(78)

| bj can be inverted. If that Perhaps the matrix having the elements bi | A were the case then we would reach a contradiction: we could conclude that A has an inverse and also that it does not have an inverse. We are saved however by a theorem that says that the determinant of the matrix representing an is the same regardless of the representation used to obtain the operator A matrix. 10 Numerical error. We calculate the inverse of a matrix by numerical methods. Sometimes these methods fail to nd the correct solution of a system of equations. This happens because the matrix is such that the inversion procedure generates large round-o errors. This, in turn, happens when the eigenvalues of the matrix dier from each other by many orders of magnitude. In such a case, the matrix is said to be ill-conditioned. Special procedures exist for dealing with ill-conditioning. Whenever you calculate an inverse of a matrix it is good practice to check whether it satises Eqs. 62 and 63. The function Inverse[M ] in Mathematica gives the inverse of matrix M , and it gives an error message if the inverse does not exist or if the matrix is ill-conditioned. Exercise 4 Calculate the inverse of

3 1 2 1 1 0 2 0 1 Test that the inverse has all the properties derived above.

6. Operator Representation, December 14, 2009

16

11 Unitary matrices. We dened a unitary operator through the equation = U

N n=1

|un un un |

(79)

where |un , n = 1, . . . , N is an orthonormal basis set and Here |un | u n un is the absolute value of the complex number un . The condition in Eq. 80 is equivalent to un = ein , (81) |un | = 1 (80)

where n is a real number. Furthermore, we have shown, by direct use of Eq. 79 and the denition n |un u of the adjoint U n un |, that U =U U = I if and only if U is unitary U Eq. 82 implies that = U 1 if and only if U is unitary U (83) (82)

= U 1 is used to dene unitary operators. In many textbooks the relation U ? Let us What do these properties mean for the matrices representing U look at Eq. 82 in A-representation: U | am = an | I | am = nm an | U I can also write U | am = an | U I U | am = an | U
p

(84)

| ap ap | U | am an | U

(85)

But the matrix of an adjoint operator satises | ap = U an | ap = ap | U | an (U )np an | U

= Upn

(86)

6. Operator Representation, December 14, 2009

17

Using this in Eq. 85 gives U | am = an | U Now use Eq. 87 in Eq. 84 to obtain

Upn Upm = mn p Upn Upm p

(87)

(88)

Remember that in the symbol Upm , p labels the rows of the matrix and m labels its columns. The sum in Eq. 88 is over the rows. We can think of the mth column {U1m , U2m , . . . , UN m } as forming a vector v(m) with components v(m) {U1m , U2m , . . . , UN m } Eq. 88 can then be written as v(n) | v(m) = mn (89)

is unitary and U is the matrix representing Thus we can rephrase Eq. 88: if U it, the vectors formed with the rows of U are orthonormal. U = I , we can show that the vectors formed with the Similarly, using U are orthonormal. columns of a matrix representing a unitary operator U N = n=1 |un un un | with the requirement that un = The denition U exp[in ], with n real, tells us that the determinant of the matrix representing in a complete orthonormal basis is U
N

det U = u1 u2 uN = exp[i

n ]
n=1

(90)

(since the determinant is the product of the eigenvalues). Therefore the absolute value of the determinant of a matrix representing a unitary operator is equal to 1.