# 13 Addition of angular momenta

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1 TFY450/FY045 Tillegg 13 - Addition of angular momenta 1 TILLEGG Addition of angular momenta (8.4 in Hemmer, 6.10 in B&J, 4.4 in Griffiths) Addition of angular momenta enters the picture when we consider a system in which there is more than one contribution to the total angular momentum. If we consider e.g. a hydrogen there are contributions both from the spin of the electron and the orbital motion. Even in the case when the latter is zero there are two contributions to the total angular momentum, because the proton spin can of course not be neglected. We shall now see how these contributions to the total angular momentum add, that is, we shall derive the rules for the addition of angular momenta. It turns out that the sum of several angular momenta is quantized according to the same rules that were derived in Tillegg Introduction Classical addition of angular momenta In classical mechanics the total angular momentum of two systems with angular momenta L 1 and L is given by the vector sum L = L 1 + L : Here the size L L of the total angular momentum can vary between L 1 + L and L 1 L, depending on the angle (α) between the two vectors L 1 and L. Thus in classical mechanics L satisfies the triangle inequality L 1 L L L 1 + L. (T13.1) We shall now see that the total angular momentum is a meaningful quantity also in quantum mechanics.

2 TFY450/FY045 Tillegg 13 - Addition of angular momenta Quantum-mechanical addition of angular momenta The spins of the electron and the proton in a hydrogen atom have the same size, S e = S p = h 3/4. If we consider a hydrogen atom in the ground state, in which the orbital angular momentum iz zero, what is then the total angular momentum due to the two spins, S = S e + S p? Will this quantity vary continuously between 0 and h 3/4, as one would expect from the classical triangle inequality above? The key to the quantum-mechanical answer to this question (which definitely is no) lies in the fact that the two spins that we want to add are compatible observables. Therefore the corresponding operators, which we may denote by Ŝ1 and Ŝ, commute: [Ŝ1i, Ŝj] = 0, i, j = x, y, z. (T13.) Since each of the operators Ŝ1 and Ŝ are angular-momentum operators, i.e. satisfy the angular-momentum algebra, it is then easy to see that also the operator Ŝ = Ŝ1 + Ŝ is an angular-momentum operator (i.e. satisfies the angular-momentum algebra). We have e.g. [Ŝx, Ŝy] = [Ŝ1x + Ŝx, Ŝ1y + Ŝy] = [Ŝ1x, Ŝ1y] + [Ŝx, Ŝy] = i hŝ1z + i hŝz = i hŝz. (T13.3) But then our theory of angular momenta enters with full force. According to this theory, the possible eigenvalues of Ŝ = (Ŝ1 + Ŝ) are h s(s + 1), where anything but integer or half-integer quantum numbers s are excluded. In the case at hand we shall see that the possible values are s = 0 and s = 1. According to the measurement postulate a measurement of S e + S p for the hydrogen ground state must then give either 0 or h, in sharp contrast to the classical triangle inequality. In the next section, we shall show why the addition two spins 1 must give either s = 0 or s = Addition of two spins 1 Instead of measuring the total spin S 1 + S and its z-component S z, we can choose to measure the z-components of each of the two spins. (The two spins are compatible; the four operators Ŝ1z, Ŝz, Ŝ 1 and Ŝ all commute with each other.) Such a measurement will leave the system in in one out of four states which can be represented by abstract vectors in the following way:

3 TFY450/FY045 Tillegg 13 - Addition of angular momenta 3 Here, 1 e.g. stands for a state in which spin no 1 is up and spinn no is down. We then have We also note that for this state Ŝ 1z = (Ŝ1z 1 ) = 1 h, (m 1 = 1 ) Ŝ z = 1 (Ŝz ) = 1 h (m = 1 ). Ŝ z = (Ŝ1z + Ŝz) = 0 (m = m 1 + m = 0). Thus the four states are eigenstates also of Ŝz = Ŝ1z + Ŝz, with quantum numbers m = m 1 + m = 1, 0, 0 and 1, as indicated in the figure above. The four states above together constitute a complete set of states for this two-spin system. Therefore they can be used as a four-dimensional basis, in terms of which any state for this system can be described. This means e.g. that the possible eigenstates s, m of the operators Ŝ and Ŝz for the total spin can be expanded in terms of the four basis states above, which we from now on may call the old states. We must expect to find four such new states s, m, which can be expressed as linear combinations of the old states,, and. The quantum numbers m found above bring us a long way towards the solution of this mystery, telling us that it is possible to find one new state with m = 1, one with m = 1 and two with m = 0. Then we don t need much fantasy to guess that the new states are a triplet of states with s = 1 : 1, 1, 1, 0 and 1, 1, together with a singlet with s = 0 : 0, 0. These guesses are easily verified, because the old state is the only one with m = 1, we must expect that this state is the upper rung in a triplet ladder, with s = 1, that is an eigenstate Ŝ with eigenvalue h. This is verified by using equation (T11.37) from Tillegg 11, on the form Ŝ = Ŝ z + hŝz + Ŝ Ŝ+ = Ŝ z hŝz + Ŝ+Ŝ. (T13.4) The first of these equations gives Ŝ = (Ŝ z + hŝz + Ŝ Ŝ+) = ( h + h h) + Ŝ (Ŝ1+ + Ŝ+) 1 = h, q.e.d., (T13.5) since Ŝ1+ 1 = 0 and Ŝ+ = 0. (See the figure on page 11 in Tillegg 1.) Thus, if we prepare the state by measuring S 1z and S z, we have in fact prepared a state with s = 1 and m = 1; The upper rung in the triplet ladder is 1, 1 =. In the same manner we have that Ŝ = (Ŝ z hŝz + Ŝ+Ŝ ) = [ h h( h)] + Ŝ+(Ŝ1 + Ŝ ) 1 = h. (T13.6) So the lower rung in the triplet aldder is 1, 1 =. The moral so far is that the two states and with extreme m-values (m = 1 and m = 1) are also eigenstates of Ŝ and Ŝz (in addition to being eigenstates of Ŝ 1, Ŝ, Ŝ1z and Ŝz), and are the upper and lower rungs in a triplet ladder.

4 TFY450/FY045 Tillegg 13 - Addition of angular momenta 4 We can find the central rung in the triplet ladder by using the ladder operator Ŝ. From (T11.5) we have that Ŝ ± s, m = h (s m)(s + 1 ± m) s, m ± 1, (T13.7) which provide us with the following useful formulae: Ŝ 1, 1 = h 1, 0 (T13.8) and [cf (T1.1)] Ŝ 1 1 Ŝ1 1, 1 = h 1 and Ŝ = h. (T13.9) This gives for the central rung: 1, 0 (8) 1 = h Ŝ 1, 1 = 1 h (Ŝ1 + Ŝ ) 1 1 = h [(Ŝ1 1 ) + 1 (Ŝ )] (9) = 1 [ ] 1 ( + ). (T13.10) (T13.11) We observe that this is a 50/50 linear combination of the old states with m = 0. This completes the triplet ladder. A small exercise: (1) Check that 1, 0 is normalized. () According to equation (T13.7), 1, 1 = Ŝ 1, 0 /( h ). Check that this formula gives the correct result. (3) If the state 1, 0 is prepaered by a measurement of S and S z, what is then the probability that a new measurement of S 1z gives + h? 1 Now it only remains to find the singlet, the state with s = m = 0 (a ladder with only one rung). This state too must be a linear combination of the two states and with m = 0, while it is orthogonal to 1, 0 (because the quantum numbers s are different). Orthogonality is achieved simply by repacing the plus sign between the two trems by a minus sign: 0, 0 = 1 ( 1 1 ) 1 ( ). (T13.1) A small exercise: Check that this state is an eigenstate of with eigenvalue equal to zero. [Hint: Ŝ+ = Ŝ1+ + Ŝ+.] Ŝ = Ŝ z + hŝz + Ŝ Ŝ+

5 TFY450/FY045 Tillegg 13 - Addition of angular momenta 5 Conclusion and comments (i) By measuring both S 1z and S z we can prepare the two-spin system in one of the old states, 1, 1, 1, 1. In these states S 1z and S z have sharp values, and so does S z. (ii) For these old states S is not sharp, except for 1 and 1, which happen to be the upper and lower rungs in the triplet ladder. The reason that S is not sharp for the other old states ( 1 and 1 ) is that Ŝ does not commute with Ŝ1z and Ŝz. (iii) If we choose instead to measure S z and S, this spin system is prepared in one of the new states, either in one of the triplet states 1, 1 = 1, 1, 0 = 1 ( ), 1, 1 = 1, (triplet) (T13.13) or in the singlet, 0, 0 = 1 ( 1 1 ). (singlet) (T13.14) Here S 1z and S z are unsharp, except in the two states 1 and 1. The figure below gives an illustration of both the old and the new states. Remember: The old states on the left are prepared by measuring S 1z and S z separately. The new states on the right are prepared by measuring the size S and the z-component S z of the total spin. (iv) The singlet corresponds to S = 0, which means that the two spins S 1 and S are antiparallel. The triplet corresponds to an angle α = arccos / between the two vectors S 1 and S. This is the closest the two spins come to being parallel.

6 TFY450/FY045 Tillegg 13 - Addition of angular momenta 6 (v) The old and the new sets of states are both perfectly applicable as basis sets for this two-spin system. We note, however, that the triplet and singlet states are respectively symmetric and antisymmetric with respect to the interchange of the particle indices 1 and. This is important when the two particles (fermions) are identical. Then the total state is required to be antisymmetric with respect to interchange. This can be achieved either by combining a triplet spin state with a spatial wave function that is antisymmetric with respect to interchange, or by combining the antisymmetric singlet state with a symmetric spatial wave function. A small exercise: Express the old states 1 and 1 in terms of the new states 0, 0 and 1, 0. If we prepare 1 by a measurement of S 1z and S z, what are then the possible results of a new measurement of S z and S, and what are the probabilities for these results? 13.3 General addition of angular momenta It is easy to generalize the treatment above so that we can combine any two angular momenta. If j 1, m 1 (m 1 = j 1, j 1 + 1,..., j 1 ) is a multiplet of eigenstates of the angular-momentum operators Ĵ 1 and Ĵ1z, and j, m (m = j, j + 1,..., j ) is a multiplet of eigenstates of Ĵ and Ĵz, then we have a set of (j 1 + 1)(j + 1) old states of the type j 1, m 1 j, m. The quantum numbers m 1, m and m = m 1 +m of these states are illustrated on the left in the figure below for the case j 1 = 3, j =, which gives 7 5 = 35 old states.

8 TFY450/FY045 Tillegg 13 - Addition of angular momenta 8 We sam an example of this in the addition of two spins 1. These coefficients are called Clebsch Gordan coefficients. This example illustrates the general rules for the addition of two angular momenta, which are: When j 1 and j are added, the maximal and minimal values of j are j max = j 1 + j, j min = j 1 j, (T13.15) and the allowed j-values in this interval are j = j 1 j, j 1 j + 1,, j 1 + j. (T13.16) We note that if both j 1 and j are half-integral, or if both are integers, then the possible quantum numbers j are integers. In the opposite case, when when either j 1 or j is halfintegral while the other one is an integer, the resulting j-values become half-integral. Note also that it is the quantum numbers that enter the triangular inequality this time (not the sizes Ĵ1 and Ĵ, as we had in the classical case): j 1 j j j 1 + j. ( (triangular inequality) ) (T13.17) This method can easily be generalized to more than two angular momenta. One starts with combining J 1 and J. Then the sum J 1 of these is combined with J 3, etc Commutation rules Let us summarize the commutation rules for the two angular momenta that were added. In analogy with (T13.), the two operators Ĵ1 and Ĵ commute. Since the three operators Ĵ 1, Ĵ and Ĵ = Ĵ1 + Ĵ all satisfy the angular-momentum algebra, it follows in the usual way that [Ĵ 1, Ĵ1] = 0, [Ĵ, Ĵ] = 0 and [Ĵ, Ĵ] = 0. It should be noted that also Ĵ 1 and Ĵ commute with Ĵ and Ĵz: [Ĵ, Ĵ 1] = [Ĵ, Ĵ ] = 0, [Ĵz, Ĵ 1] = [Ĵz, Ĵ ] = 0. [Show this by using that Ĵ = Ĵ 1 + Ĵ + Ĵ1 Ĵ.] Thus, in the new states j, m, not only J = h j(j + 1) and J z = hm are sharp, but also J 1 = h j 1 (j 1 + 1) and

9 TFY450/FY045 Tillegg 13 - Addition of angular momenta 9 J = h j (j + 1). It is customary to state that j 1 and j are good quantum numbers in the new states, in addition to j and m. We should also note that the coupling term Ĵ1 Ĵ has sharp values in the new states. Using the relation Ĵ1 Ĵ = 1 (Ĵ Ĵ 1 Ĵ ), we find that this coupling term commutes withall the operators Ĵ 1, Ĵ, Ĵ and Ĵz: [Ĵ1 Ĵ, Ĵ 1] = [Ĵ1 Ĵ, Ĵ ] = [Ĵ1 Ĵ, Ĵ ] = [Ĵ1 Ĵ, Ĵz] = 0. (T13.18) And for a state with quantum numbers j, m, j 1 and j we then have that J 1 J = 1 (J J 1 J ) = 1 h [j(j + 1) j 1 (j 1 + 1) j (j + 1)] (T13.19) is sharp. On page 4 we stressed that Ŝ does not commute with Ŝ1z and Ŝz. This is shown as follows: This can be generalized to [Ĵ, Ĵ1z] = [Ĵ 1 + Ĵ + (Ĵ1xĴx + Ĵ1yĴy + Ĵ1zĴz), Ĵ1z] = [Ĵ1x, Ĵ1z]Ĵx + [Ĵ1y, Ĵ1z]Ĵy + 0 and then you will probably be able to argue that From Ĵ = Ĵ 1 + Ĵ + Ĵ1 Ĵ it then follows that so that = i hĵ1yĵx + i hĵ1xĵy = i h(ĵ1 Ĵ) z. (T13.0) [Ĵ, Ĵ1] = i h(ĵ1 Ĵ), (T13.1) [Ĵ, Ĵ] = i h(ĵ1 Ĵ). (T13.) [Ĵ1 Ĵ, Ĵ1] = i h(ĵ1 Ĵ) and [Ĵ1 Ĵ, Ĵ] = i h(ĵ1 Ĵ), (T13.3) [Ĵ1 Ĵ, Ĵ] = 0. (T13.4) Well, this was quite a few formulae, but it may be practical to have them collected this way, for possible future reference Addition of orbital angular momentum and spin An important example (e.g. if we want to study the hydrogen atom more closely) is the addition of the orbital angular momentum L and the spin S of the electron: J = L + S. (T13.5) The triangular inequality (T13.17) then gives half-integral values for the quantum number j for the total angular momentum J = L + S: l 1 j l + 1. For l = 0, we have J = S and j = s = 1, so that we have two states, with J z = 1 hm = ± h. (Here, the magnetic quantum number m denotes the z-component of the total angular momentum.)

10 TFY450/FY045 Tillegg 13 - Addition of angular momenta 10 For l 1 we have two possible values for j, namely j = l + 1 and j = l 1. j = l + 1 : In this case L and S are as parallel as they can possibly be (for a given l). As illustrated in the figure, the angle α between L and S then is not equal to zero: j = l 1 : In this case L and S are as antiparallel as they can possibly be (for a given l): In both these cases, j and l are good quantum numbers. This means that the angle α between L and S can be calculated by means of the relation J = L + L S + S, which gives L S = 1 (J L S ) = 1 h [ j(j + 1) l(l + 1) 3/4]. (T13.6) This relation is a special case of (T13.19) Addition of several angular momenta The rules given above can also be used when there are more than two contributions to the total angular momentum of a system: J = J 1 + J + J 3 +. We may then start by combining J 1 and J to J 1 = J 1 + J. The possible quantum numbers j 1 are then limited by the triangular inequality: j 1 j j 1 j 1 + j. We continue by combining J 1 with J 3, and again use the triangular inequality. Continuing this process, we end up finding all possible values of the resulting quantum number j. An example is

11 TFY450/FY045 Tillegg 13 - Addition of angular momenta 11 Nuclear spin With the exception of ordinary hydrogen, all atomic nuclei consist of Z protons and N = A Z neutrons, where A is the nucleon number. The total angular momentum of a nucleus A Z X is called the nuclear spin and is denoted by an angular-momentum (spin) quantum number I. Thus, a single proton or a single neutron has I = 1. Let us now see what the rules for the addition of angular moenta have to say about the spin quantum number I of the next nucleus, the deuteron the stable nucleus of deuterium, 1H, heavy hydrogen. There are in principle three contributions to the total angular momentum I (the spin) of the deuteron. These are the spins S p and S n of the proton and the neutron and a possible orbital aangular momentum L of the proton-neutron system: I = S p + S n + L. If we first imagine the two spins combined to S = S p + S n, then this can result either in a triplet, characterized by the quantum number S = 1, or a singlet with S = 0. 1 Thus we have two possibilities for the spin. Furthermore, from the addition rules for angular momenta we can not rule out the possibility that the nutron-proton system in its ground state has a non-zero orbital angular momentum, characterized by an integer quantum number L. When this is combined either with S = 0 or S = 1, it follows that the deuteron must have an integer quantum number I. This is as far as the addition rules can take us. Experimentally it turns out that the spins of the proton and the neutron together form a triplet, S = 1, while the resulting angular-momentum quantum number of the deuteron is I = 1 (spin 1). The addition rules then limit the orbital angular-momentum quantum number to the values L = 0, 1,. (All these can be combined with S = 1 to the resultant I = 1.) Here it turns out that L = 1 is excluded (for reasons that we cannot enter into here). Then two possibilities remain, one with L = 0 and one with L =. Experimentally it turns out that the deuteron is in a superposition of these two states; L = 0 is the dominating contribution, but there is also a small admixture of L =, which results in a ground state for the deuteron deviating slightly from being spherically symmetric. This deviation is an experimental fact. From the discussion above, we understand that the spin quantum number (I) for a heavier nucleus must be an integer for a nucleus with even nucleon number A and half-integral for a nuleus with odd A. Of the nuclei with even A it turns out that almost all have I = 0. The exceptions are nuclei for which both N and Z are odd. In addition to the deuteron 1H (I = 1), there are only a few such nuclei which are stable, two of which are 6 3Li (I = 1) and 14 7 N (I = 1). But 1 When the spins or orbital angular momenta of several particles are added, it is customary to use capital letters for the quantum numbers, S = h S(S + 1), L = h L(L + 1). It is also usual to use the capital letters S,P,D,F,G,H for states with L = 0, 1,, 3, 4, 5, in analogy with the symbols used s,p,d,f,g,h for one-particle states with l = 0, 1,, 3, 4, 5. It may perhaps be somewhat confusing to learn that the ground state does not have a sharply defined orbital angular momentum. This has to do with the fact that the strong nuclear force, which provides the binding, is described by a model with a non-central potential. Then L does not commute with the Hamiltonian operator, and L is not a so-called good quantum number.

12 TFY450/FY045 Tillegg 13 - Addition of angular momenta 1 there are of course many unstable odd-odd nuclei. An example is the cobalt isotope 60 7Co with a life-time of around five years, which has I = 5. Examples of nuclei with odd nucleon numbers are the iron isotopes 55 6Fe (I = 3/, τ =.7 years) and 57 6Fe (I = 1 59, stable), and the stable cobalt isotope 7Co, which has I = 7/. Another example is the relatively rare helium isotope 3 He (helium-3) which has I = 1. From what was stated above it follows that all nuclei for which both Z and N are even have spin zero (I = 0). An example is the α particle, the nucleus of 4 He. Resulting spin, orbital angular momentum and total angular momentum for atomic electrons As an example we may consider carbon, with the electron configuration 1s s p in the ground state. The spins and the orbital angular momenta in the closed 1s and s shells both add up to zero. Therefore, the quantum numbers S, P and J for the total spin, the total orbital angular momentum and the total angular momentum of the six electrons in carbon are determined by the two p electrons. For the two spins there are two possibilities: They can either form a singlet (S = 0) or a triplet (S = 1). If they are in the singlet state, we remember from the explicit construction of this state that it it is antisymmetric with respect to interchange of the two electrons. The Pauli principle then requires that the spatial state of the two electrons is symmetric. (We remember that the total state of the two identical electrons must be antisymmetric with respect to interchange of the particle indices, according to Pauli s exclusuion principle.) Carrying through the coupling of the spatial states with l 1 = 1 and l = 1 explicitly, one finds (cf exercise) that the resulting spatial states for L = 1 are antisymmetric, while the states for L = 0 and L = are symmetric with respect to interchange. Thus the states with L = 0 and L = can be combined with the singlet spin state. The resulting total states are denoted respectively by 1 S 0 and 1 D. Here the upper index gives the spin multiplicity S + 1. The letters S and D signify that the total orbital angular momentum quantum number L is respectively zero and. The lower index is the quantum number J, which here equals L, since S = 0. Thus the notation is S+1 (L letter) J. The other possibility is that the spins form a triplet (S = 1) (which is symmetric with respect to interchange). The only possibility for the orbital quantum number L then is L = 1, so that the state is characterized by 3 P J. On combining S = 1 and L = 1 we have three possibilities for the quantum number J of the total angular momentum: J = 0, 1,. Experiments show that the lowest energy for the carbon atom (and hence the ground state) is obtained when S = 1, L = 1 and J = 0. So, the ground state for carbon can be denoted by 3 P 0. The table below shows the configuration and the resulting quantum numbers L, S and J for a selection of elements. Here we see that helium, neon and all the other noble gases have 1 S 0, that is a total spin S = 0, total orbital angular momentum L = 0 and hence also total angular momentum J = 0. In view of this, it is perhaps not very strange to find that the alkali metals sodium and potassium etc, with one electron in an s-state outside filled shells, get the same quantum numbers as hydrogen, namely S 1/.

13 TFY450/FY045 Tillegg 13 - Addition of angular momenta 13 Ground-state configuration for some elements Z Element Configuration Symbol 1 H 1s S 1/ He (1s) 1 S 0 3 Li [He](s) S 1/ 4 Be [He](s) 1 S 0 5 B [He](s) (p) P 1/ 6 C [He](s) (p) 3 P 0 7 N [He](s) (p) 3 4 S 3/ 8 O [He](s) (p) 4 3 P 9 F [He](s) (p) 5 P 3/ 10 Ne [He](s) (p) 6 1 S 0 11 Na [Ne](3s) S 1/

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