Spherical Tensor Operators in NMR

Muhammad Sabieh Anwar March 5, 2004
1. Quick Review of Vector Operators: Considering an infinitesimal rotation through δ ˆ ˆ ˆ ˆ about the axis Ju = J.u, the components of a vector operator V, transform Vi → Vi according to the following transformation rules: ˆ D(R) ˆ Vi − − Vi −→ = = Moreover ˆ D † (R)Vi D(R) =
j

ˆ D(R)Vi D † (R) δ ˆ ˆ ˆ Vi − i [ Vi , J u ] h ¯ ˆ Rij Vj δ ˆ 1 − exp (−i Ju ) h ¯

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

also D(R) =

(1d)

The equality in (1c) holds because of the following concepts: ˆ (a) The expectation value of a component α|Vi |α remains unchanged in the rotated frame ˆ ˆ (with respect to the transformed operator), i.e., α |Vi |α = α|Vi |α where |α −→ ˆ D(R)|α = |α 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 ˆ ˆ system, including the measuring apparatus. In such a scenario, Vi |α = Vi |α . ˆ (b) The expectation value α|Vi |α is unchanged with respect to transformed operator and kets, but with respect to the kets and operators in the un-rotated frame, it transˆ ˆ forms like the components of a cartesian vector, i.e., α|Vi |α −→ j Rij α|Vj |α = ˆi |α = α|D † (R)Vi D(R)|α . This last equation is not to be confused with the ˆ α |V ˆ ˆ equality α |Vi |α = α|Vi |α , in which both the operator and the kets are transformed. (c) Since the matrix with elements Rij is orthogonal, i.e., be written as: ˆ D(R)Vi D † (R) =
j k

Rik Rjk = δij , (1c) can also

ˆ Vj Rji

(1e)

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

1

such that D − = − . we can define a tensor operator T with components {Ts } which transforms according to the equation: ˆ Ts Ds. In general Hilbert space.The defining transformation rule for vector operators can also be written in a more compact form: ˆ ˆ [Vi . we continue: − → |ψ (→ ) = |ψ(D −1 − ) r r → → As − is just an arbitrary variable. We define the transformation of the state |ψ → |ψ . Jj ] = i¯ h ijk Vk ˆ (1f) We have observed that scalar and vector operators are defined through the behaviour under rotations. It expresses our intuition that all observables and spectra of eigenvalues remain unchanged when both the variable and the ˆ ˆ state are rotated: the same idea as has been expressed in [1b] as α |Vi |α = α|Vi |α . however it pays to focus on just either of the two! Consider a state represented by a ket |ψ in the Hilbert → space. If we are considering rotations in the real. the r r state will also have been modified. which involve a rotation of the co-ordinate axes – affording what is called a basis transformation. 3. We shall be concerned with passive rotations.i (R) Ti −→ Ti = D(R)Ti D † (R) = (3) s 2 . This state will be depend on a dynamic variable. like the position co-ordinate − . Moreover from the last r r equality in (2c). Cartesian Tensor Operator Motivated by the definition of a vector operator presented in (1e) . we can replace it by − : r r → → → |ψ (− ) = |ψ(D −1 − ) = D|ψ(− ) r r r (2c) (2b) → − D is unitary because the norms of D|ψ − and |ψ → are the same. In the new basis. all elements of the matrix representing D are real and hence its representation is a symmetric matrix. the matrix representation of an arbitrary rotation R is denoted as D(R). A r − ) . 2. such that: → → |ψ (− ) = |ψ(− ) r r (2a) (2a) would strictly be true upto some global phase e iφ . We assume that this rotation in the physical r r → → space is represented by a rotation matrix D. note that we are using the same rotation matrix D for rotations of both the co-ordinates and the states. From (2a). Likewise we can also define tensor operators by characterizing their behaviour under transformations — scalar and vector operators being particular cases of these tensor operators (ranks 0 and 1 respectively). 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. Now we rotate the co-ordinate axes such → complete description of the state is thus |ψ( r − → that the position vector transforms as → → − . Another confusion arises because of the possibility of active and passive rotations. physical space. The active conceptualism is totally equivalent.

m l. Taking the inner product with the bra l. φ) = n|l. because of the invariance of the E (l) sub-space. however is not irreducible and it is not ˆ ˆ convenient to work with it. m |D(R)|l. j = 1. m ˆ n|l. m|. m|ˆ n ˆ n |l.W ( Vi W j − W i Vj ) Vi Wj + Wi Vj V.m (R) n l (6b) 5. Transformation of Spherical Harmonics under Rotations The spherical harmonic function parametrically depends on the angles θ and φ in the spatial co-ordinate basis and is given by the wavefunction representation in space as: ˆ Ylm (θ. a tensor product (or antisymmetric tensor of rank 1) and a traceless.q (R) (7b) 3 . we arrive at the relationship: n n = = =⇒ Ylm (ˆ ) = n = m l. m (6a) where in (6a).ˆ ˆ Given two vector operators V and W. m|D(R)|ˆ n † ˆ n|D(R) |l. 3. 1 and 2 are 1. 2. we obtain the following definition of a tensor operator of rank k: k k D(R)Tq D † (R) = q =−k k Tq Dqk. we have suppressed the sum over all possible values of l.q (R)Tq (7a) If we write the transpose of (7a). This cartesian tensor. m ˆ n|D(R)† |l. In fact the irreducible tensor operators transform just like the spherical harmonic functions and hence they are most often called the spherical tensor operators. 3 and 5 respectively. 4. which add up to 9. m l. symmetric tensor of rank 2 as expressed below: ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ V. 1 and 2. Finally (6a) can written in the more amenable form as: Ylm (ˆ ) = n m Ylm (ˆ )Dm . m (5) ˆ where n is a unit vector that points in the θ. we can form a cartesian tensor with 9 components ˆ ˆ Vi Wj where i. we can define 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. The component Vi Wj can be reduced into a scalar.φ direction. These numbers correspond well to 2l + 1 components of the spherical harmonic functions Ylm of rank l where l = 0.W ˆ ˆ Vi Wj = δij + + − δij 3 2 2 3 (4) The number of components corresponding to these tensors of ranks 0. Now consider the rotation |ˆ −→ n |ˆ = D(R)|ˆ . Definition of Spherical Tensor Operators Being motivated by the transformation relations of tensors (3) and spherical harmonics (5).

The coefficients a and b above will be determined by the normalization of the tensor operators. A simple recipe for the formation of tensor operators is by using the the general forms of the spherical tensor operators.S. we can find the following so-called standard components of A that transform like the components of a rank 1 tensor. We n n consider the example of the formation of the components of a rank 1 tensor operator from the spherical harmonics Y10. Jz } form a C. Ylm (θ. i. x = r cos φ sin θ.O. for example. φ) = Ylm (ˆ ) that are generally n ˆ ˆ presented in standard tables. Vy . such that {H. (ˆ )x = x/r → Vx and (ˆ )y = y/r → Vz . Ay . ˆ ˆ ˆ with components {Vx .. Az }. we have also made use of the substitutions commonplace in the spherical coordinate system. y = r sin φ sin θ and z = r cos θ.±1 : T01 T11 1 T−1 = = = ˆ Az 1 ˆ ˆ − √ (Ax + iAy ) 2 1 ˆ ˆ √ (Ax − iAy ) 2 (9a) (9b) (9c) It can be verified that this spherical tensor operator of rank 1 satisfies the commutation relations given in (8). Some authors prefer to q use the notation Tk . We need to ˆ ˆ re-normalize because we have replaced a unit vector n by an arbitrary vector V. Tq ] = and k ˆ [J± .k Note the similarity of (7b) with (1e). T10.±1 : 3 3 z cos θ = 4π 4π r 3 ±iφ 3 x ± iy e sin θ = 8π 8π r Y10 = =⇒ =⇒ ˆ T01 = aVz T0±1 = ˆ ˆ b (Vx ± Vy ) (10a) (10b) Y1±1 = In deriving (10). The tensor operators Tq transform in a similar fashion m to the spherical harmonic wavefunctions Yl with k = l and q = m. Construction of Higher Rank Tensors We can also extend the same technique to generate tensor of any higher rank. ˆ ˆ ˆ J2 . Tq ] = ¯ q Tq h k ¯ h k k(k + 1) − m(m ± 1) Tq±1 (8a) (8b) ˆ 6. These components do not form an irreducible representation. where α represents the eigenvalues of the operator H. 7. Spherical Tensor Operator Reduction of a Rank 1 Tensor (Vector) A vector A ˆx .e. Vz }. analogous to the relation given in (1f) is given by the following commutation rleations that must be satisfied by a tensor operator: ˆ k [Jz . whereas I shall use the former. The unit vector n can be replaced by an arbitrary vector V.C. we can consider the formation of the components 4 . A straightforward but useful point to remember is that the spherical tensor operators are ˆ ˆ irreducible in standard E (α. A more convenient operational definition of a spherical tensor operator. The individual components of the unit vector are replaced ˆ n ˆ ˆ according to the relations (ˆ )z = z/r → Vz . 8. ˆ ˆ has components {A ˆ However. J) basis.

m1 . 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. q1 . m1 . q2 |k1 . k. q can be recognized to be the Clebsch-Gordon coefficient C(j1 . J = k and M = q. j2 .of a rank 2 tensor: Y2±2 = = =⇒ 15 ±2iφ e sin 2 θ 32π 15 x2 − y 2 ± 2ixy 32π r2 ±2 ˆ ˆ 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 . (See the document ”Superoperators in NMR” for a discussion of operators and superoperators). The similarity of (11) with the relationship between the direct product and total angular momentum bases must be appreciated: |J. m2 . k2 . . Each basis provides its own set of merits and demerits. 1. For a single spin 1/2 the tensor operators in the Zeeman basis are simply: T00 = T01 T11 1 T−1 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) 5 . m2 = q2 . J. J. j2 . k2 . where N is the number of spins. M = m1 m2 j1 . employing the same C-G co-efficients. j2 . q2 |k1 . Spherical Tensor Operator Basis for NMR Different operator bases for an NMR system can be constructed. m2 |j1 . This co-efficient will be non-zero only if q = q1 + q2 . Both methods are essentially the same. k2 . we shall obtain basis tensor operators of ranks 0. One useful basis is the set of spherical tensor operators. j2 . j2 = k2 . k. m2 (12) It follows from (11) and (12). M |j1 . . if we are only considering 1/2 spins. 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. For an ndimensional system we need n2 (= 4N ) operators in the operator space. For a system of spin with a single spin I. . Moreover the inner product k1 . m1 . 9. k2 . M ) with j1 = k1 . . 2I. m1 = q1 . q1 .

Inspection shows that they will be of ranks k = 0. a single spin 1 will have a set of 9 basis operators. 2 and 3. in accordance with the Condon-Shortley phase convention for spherical harmonics: k k (Tq )† = (−1)q T−q (15) Equipped with the conditions set forth in (14) and (15).) As an additional example. we can derive all spherical tensor basis operators. 6 . For example.While constructing spherical tensor operators. using (11). We need 16 tensor operators. and the commutation relations given in (8). 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 T−1 = √ 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 T−1 = − √ 1 0 0 = (−1)−1 (T12 )† 2 0 −1 0   0 0 0 2 T−2 = 0 0 0 = (−1)2 (T22 )† 1 0 0 (16 contd. defined as: T r(Ui† Uj ) = δij (14) Moreover the following phase convention is respected for tensor operators. we make note of the fact that the operators must form an orthonormal set. 1. let us construct the spherical operators for the two-spin case.

Liouville Equation of Motion.I. Addison-Wesley Publishing. Vol. 2. 8. pp152). Mag.. (Ch6. Sec. Quantum Mechanics Vols.. Quantum Mechanics.. Quantum Mechanics.References 1. et.J.. 1961. 5. Mayne C. Messiah A. Nucl. 1 and 2. Encycl. Res. 7 . 2. Ch. McGraw Hill Book Company. Sakurai J..L. Tannoudji C.A. 1968. Ch. 28. 1994 (Ch3. North Holland Publishing Compnay. 3. Modern Quantum Mechanics... 2717-2730.7. 10). Schiff L. Potter J. al. 4.

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