Spherical Tensor Operators in NMR

Muhammad Sabieh Anwar March 5, 2004

D(R)Vi D (R) Vi i [ Vi , J u ] h Rij Vj 1 exp (i Ju ) h

(1a) (1b) (1c)

also D(R) =

(1d)

The equality in (1c) holds because of the following concepts: (a) The expectation value of a component |Vi | remains unchanged in the rotated frame (with respect to the transformed operator), i.e., |Vi | = |Vi | where | D(R)| = | and Vi is the operator transform. The expectation value in the two bases must be the same, because we are assuming that space is isotropic, and all physical observables and physical laws must remain invariant under the rotation of the entire system, including the measuring apparatus. In such a scenario, Vi | = Vi | . (b) The expectation value |Vi | is unchanged with respect to transformed operator and kets, but with respect to the kets and operators in the un-rotated frame, it trans forms like the components of a cartesian vector, i.e., |Vi | j Rij |Vj | = i | = |D (R)Vi D(R)| . This last equation is not to be confused with the |V equality |Vi | = |Vi | , in which both the operator and the kets are transformed. (c) Since the matrix with elements Rij is orthogonal, i.e., be written as: D(R)Vi D (R) =
j k

Rik Rjk = ij , (1c) can also

Vj Rji

(1e)

The above equation will be used as our starting point for dening tensor operators.

The dening transformation rule for vector operators can also be written in a more compact form: [Vi , Jj ] = i h
ijk Vk

(1f)

We have observed that scalar and vector operators are dened through the behaviour under rotations. Likewise we can also dene tensor operators by characterizing their behaviour under transformations scalar and vector operators being particular cases of these tensor operators (ranks 0 and 1 respectively). 2. Elaboration of point (b) Rotations in Quantum Mechanics present some confusion because they involve a rotation of both the variables as well as the states. Another confusion arises because of the possibility of active and passive rotations. We shall be concerned with passive rotations, which involve a rotation of the co-ordinate axes aording what is called a basis transformation. The active conceptualism is totally equivalent, however it pays to focus on just either of the two! Consider a state represented by a ket | in the Hilbert space. This state will be depend on a dynamic variable, like the position co-ordinate . A r ) . Now we rotate the co-ordinate axes such complete description of the state is thus |( r that the position vector transforms as . We assume that this rotation in the physical r r space is represented by a rotation matrix D, such that D = . In the new basis, the r r state will also have been modied. We dene the transformation of the state | | , such that: | ( ) = |( ) r r (2a)

(2a) would strictly be true upto some global phase e i . It expresses our intuition that all observables and spectra of eigenvalues remain unchanged when both the variable and the state are rotated: the same idea as has been expressed in [1b] as |Vi | = |Vi | . From (2a), we continue: | ( ) = |(D 1 ) r r As is just an arbitrary variable, we can replace it by : r r | ( ) = |(D 1 ) = D|( ) r r r (2c) (2b)

D is unitary because the norms of D| and | are the same. Moreover from the last r r equality in (2c), note that we are using the same rotation matrix D for rotations of both the co-ordinates and the states. If we are considering rotations in the real, physical space, all elements of the matrix representing D are real and hence its representation is a symmetric matrix. In general Hilbert space, the matrix representation of an arbitrary rotation R is denoted as D(R). 3. Cartesian Tensor Operator Motivated by the denition of a vector operator presented in (1e) , we can dene a tensor operator T with components {Ts } which transforms according to the equation: Ts Ds,i (R) Ti Ti = D(R)Ti D (R) = (3)
s

 Given two vector operators V and W, we can form a cartesian tensor with 9 components Vi Wj where i, j = 1, 2, 3. This cartesian tensor, however is not irreducible and it is not convenient to work with it. The component Vi Wj can be reduced into a scalar, a tensor product (or antisymmetric tensor of rank 1) and a traceless, symmetric tensor of rank 2 as expressed below: V.W ( Vi W j W i Vj ) Vi Wj + Wi Vj V.W Vi Wj = ij + + ij 3 2 2 3 (4)

The number of components corresponding to these tensors of ranks 0, 1 and 2 are 1, 3 and 5 respectively, which add up to 9. These numbers correspond well to 2l + 1 components of the spherical harmonic functions Ylm of rank l where l = 0, 1 and 2. In fact the irreducible tensor operators transform just like the spherical harmonic functions and hence they are most often called the spherical tensor operators. 4. Transformation of Spherical Harmonics under Rotations The spherical harmonic function parametrically depends on the angles and in the spatial co-ordinate basis and is given by the wavefunction representation in space as: Ylm (, ) = n|l, m (5)

where n is a unit vector that points in the , direction. Now consider the rotation | n | = D(R)| . Taking the inner product with the bra l, m|, we arrive at the relationship: n n = = = Ylm ( ) = n =
m

l, m| n n |l, m

l, m|D(R)| n n|D(R) |l, m n|D(R) |l, m n|l, m l, m |D(R)|l, m (6a)

where in (6a), we have suppressed the sum over all possible values of l, because of the invariance of the E (l) sub-space. Finally (6a) can written in the more amenable form as: Ylm ( ) = n
m

Ylm ( )Dm ,m (R) n l

(6b)

5. Denition of Spherical Tensor Operators Being motivated by the transformation relations of tensors (3) and spherical harmonics (5), we can dene a tensor operator of rank k as an operator whose 2k + 1 components transform according to the relations given below:
k k D (R)Tq D(R)

=
q =k

k k Dq,q (R)Tq

(7a)

If we write the transpose of (7a), we obtain the following denition of a tensor operator of rank k:
k k D(R)Tq D (R)

=
q =k

k Tq Dqk,q (R)

(7b)

k Note the similarity of (7b) with (1e). The tensor operators Tq transform in a similar fashion m to the spherical harmonic wavefunctions Yl with k = l and q = m. Some authors prefer to q use the notation Tk , whereas I shall use the former. A more convenient operational denition of a spherical tensor operator, analogous to the relation given in (1f) is given by the following commutation rleations that must be satised by a tensor operator:

k [Jz , Tq ] = and
k [J , Tq ] =

q Tq h k h
k k(k + 1) m(m 1) Tq1

(8a) (8b)

6. Spherical Tensor Operator Reduction of a Rank 1 Tensor (Vector) A vector A x , Ay , Az }. These components do not form an irreducible representation. has components {A However, we can nd the following so-called standard components of A that transform like the components of a rank 1 tensor, T10,1 : T01 T11
1 T1

= = =

Az 1 (Ax + iAy ) 2 1 (Ax iAy ) 2

(9a) (9b) (9c)

It can be veried that this spherical tensor operator of rank 1 satises the commutation relations given in (8). A simple recipe for the formation of tensor operators is by using the the general forms of the spherical tensor operators, Ylm (, ) = Ylm ( ) that are generally n presented in standard tables. The unit vector n can be replaced by an arbitrary vector V, with components {Vx , Vy , Vz }. The individual components of the unit vector are replaced n according to the relations ( )z = z/r Vz , ( )x = x/r Vx and ( )y = y/r Vz . We n n consider the example of the formation of the components of a rank 1 tensor operator from the spherical harmonics Y10,1 : 3 3 z cos = 4 4 r 3 i 3 x iy e sin = 8 8 r Y10 = = = T01 = aVz T01 = b (Vx Vy ) (10a) (10b)

Y11 =

In deriving (10), we have also made use of the substitutions commonplace in the spherical coordinate system, i.e., x = r cos sin , y = r sin sin and z = r cos . The coecients a and b above will be determined by the normalization of the tensor operators. We need to re-normalize because we have replaced a unit vector n by an arbitrary vector V. 7. A straightforward but useful point to remember is that the spherical tensor operators are irreducible in standard E (, J) basis, where represents the eigenvalues of the operator H, J2 , Jz } form a C.S.C.O. such that {H, 8. Construction of Higher Rank Tensors We can also extend the same technique to generate tensor of any higher rank, for example, we can consider the formation of the components 4

of a rank 2 tensor: Y22 = = = 15 2i e sin 2 32 15 x2 y 2 2ixy 32 r2 2 T2 = c (Vx iVy )2

(10c)

The following theorem helps generate an arbitrary tensor Tqk of rank k from tensors Xqk1 1 and Zqk2 with ranks k1 and k2 respectively: 2 Tqk =
q1 q2

k1 , k2 ; q1 , q2 |k1 , k2 ; k, q Xqk1 Zqk2 1 2

(11)

the indices q1 and q2 in (11) run from to k1 to k1 and from k2 to k2 respectively. Moreover the inner product k1 , k2 ; q1 , q2 |k1 , k2 ; k, q can be recognized to be the Clebsch-Gordon coecient C(j1 , j2 , m1 , m2 , J, M ) with j1 = k1 , j2 = k2 , m1 = q1 , m2 = q2 , J = k and M = q. This co-ecient will be non-zero only if q = q1 + q2 . The similarity of (11) with the relationship between the direct product and total angular momentum bases must be appreciated: |J, M =
m1 m2

j1 , j2 ; m1 , m2 |j1 , j2 ; J, M |j1 , j2 ; m1 , m2

(12)

It follows from (11) and (12), that higher rank tensors can be obtained by combining two low rank tensors in almost the same way in which two individual angular momenta are added. Both methods are essentially the same, employing the same C-G co-ecients. 9. Spherical Tensor Operator Basis for NMR Dierent operator bases for an NMR system can be constructed. Each basis provides its own set of merits and demerits. For an ndimensional system we need n2 (= 4N ) operators in the operator space, where N is the number of spins, if we are only considering 1/2 spins. (See the document Superoperators in NMR for a discussion of operators and superoperators). One useful basis is the set of spherical tensor operators. For a system of spin with a single spin I, we shall obtain basis tensor operators of ranks 0, 1, . . . , 2I. For a single spin 1/2 the tensor operators in the Zeeman basis are simply: T00 = T01 T11
1 T1

1 2 1 = 2 1 = 2 1 = 2

1 0 0 1 1 0 0 0 0 1 1 0

1 1=E 2 = Iz = I+

0 0 1 0

= I

(13)

While constructing spherical tensor operators, we make note of the fact that the operators must form an orthonormal set, dened as: T r(Ui Uj ) = ij (14)

Moreover the following phase convention is respected for tensor operators, in accordance with the Condon-Shortley phase convention for spherical harmonics:
k k (Tq ) = (1)q Tq

(15)

Equipped with the conditions set forth in (14) and (15), and the commutation relations given in (8), we can derive all spherical tensor basis operators. For example, a single spin 1 will have a set of 9 basis operators, explicitly written in the Zeeman eigenbasis as: 1 0 0 1 1 0 1 0 = 1 T00 = 3 3 0 0 1 0 1 0 1 1 T11 = 0 0 1 = I+ 2 2 0 0 0 1 0 0 1 1 T01 = 0 0 0 = Iz 2 0 0 1 2 0 0 0 1 1 1 T1 = 1 0 0 = I (16) 2 2 0 1 0 Likewise we also have the following rank 2 operators: 0 0 1 T22 = 0 0 0 0 0 0 0 1 0 1 0 0 1 T12 = 2 0 0 0 0 1 0 1 T02 = 0 2 0 6 0 0 1 0 0 0 1 2 T1 = 1 0 0 = (1)1 (T12 ) 2 0 1 0 0 0 0 2 T2 = 0 0 0 = (1)2 (T22 ) 1 0 0

(16 contd.)

As an additional example, let us construct the spherical operators for the two-spin case, using (11). We need 16 tensor operators. Inspection shows that they will be of ranks k = 0, 1, 2 and 3. 6

References 1. Sakurai J.J., Modern Quantum Mechanics, Addison-Wesley Publishing, 1994 (Ch3, pp152). 2. Tannoudji C. et. al, Quantum Mechanics Vols. 1 and 2., (Ch6, 10). 3. Messiah A.A., Potter J., Quantum Mechanics, North Holland Publishing Compnay, 1961, Vol. 2, Ch. 8. 4. Schi L.I., Quantum Mechanics, McGraw Hill Book Company, 1968, Ch.7, Sec. 28. 5. Mayne C.L., Liouville Equation of Motion, Encycl. Nucl. Mag. Res., 2717-2730.