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We are only interested in the magnetic energy states of the chain, due to the magnetic interactions of the N Fe2+ ions, each with spin 1.. We assume that ˆH1 is a small perturbation comp

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Magnetic Excitons

Quantum field theory deals with systems possessing a large number of de-grees of freedom This chapter presents a simple model, where we study the magnetic excitations of a long chain of coupled spins We show that one can associate the excited states of the system with quasi-particles that propagate along the chain

We recall that, for any integer k:

N



n=1

e2iπkn/N = N if k = pN, with p integer;

= 0 otherwise.

20.1 The Molecule CsFeBr3

Consider a system with angular momentum equal to 1, i.e j = 1 in the basis

|j, m common to ˆ J2 and ˆJ z

20.1.1 What are the eigenvalues of ˆJ2 and ˆJ z?

20.1.2 For simplicity, we shall write |j, m = |σ, where σ = m = 1, 0, −1.

Write the action of the operators ˆJ ±= ˆJ x ± i ˆ J y on the states|σ.

20.1.3 In the molecule Cs Fe Br3, the ion Fe2+ has an intrinsic angular

mo-mentum, or spin, equal to 1 We write the corresponding observable ˆ J , and

we note|σ the eigenstates of ˆ J z The molecule has a plane of symmetry, and

the magnetic interaction Hamiltonian of the ion Fe2+ with the rest of the molecule is

ˆ

H r= D

¯

h2

ˆ

J2

z D > 0

What are the eigenstates of ˆH r and the corresponding energy values? Are there degeneracies?

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204 20 Magnetic Excitons

20.2 Spin–Spin Interactions in a Chain of Molecules

We consider a one-dimensional closed chain made up with an even number N

of Cs Fe Br3 molecules We are only interested in the magnetic energy states

of the chain, due to the magnetic interactions of the N Fe2+ ions, each with spin 1

We take{|σ1, σ2, · · · , σ N }, σ n = 1, 0, −1, to be the orthonormal basis of

the states of the system; it is an eigenbasis of the operators { ˆ J z n } where ˆJ n

is the spin operator of the n-th ion (n = 1, · · · , N).

The magnetic Hamiltonian of the system is the sum of two terms ˆH =

ˆ

H0+ ˆH1 where

ˆ

H0= D

¯

h2

N



n=1

( ˆJ z n)2

has been introduced in 1.3, and ˆH1is a nearest-neighbor spin–spin interaction term

ˆ

H1= A

¯

h2

N



n=1

ˆ

J n · ˆJ n+1 A > 0

To simplify the notation of ˆH1, we define ˆJ N+1 ≡ ˆJ1.

We assume that ˆH1 is a small perturbation compared to ˆH0 (A  D),

and we shall treat it in first order perturbation theory

20.2.1 Show that 1, σ2, · · · , σ N  is an eigenstate of ˆ H0, and give the cor-responding energy value

20.2.2 What is the ground state of ˆH0? Is it a degenerate level?

20.2.3 What is the energy of the first excited state of ˆH0? What is the

degeneracy d of this level? We shall denote by E1the corresponding eigenspace

of ˆH0, of dimension d.

20.2.4 Show that ˆH1can be written as

ˆ

H1= A

¯

h2

N



n=1

1

2( ˆJ

n

+Jˆn+1

+ ˆJ − n Jˆ+n+1) + ˆJ z n Jˆz n+1

.

20.3 Energy Levels of the Chain

We now work in the subspaceE1 We introduce the following notation

|n, ± = |σ1= 0, σ2= 0, · · · , σ n =±1, σ n+1 = 0, · · · , σ N = 0.

Owing to the periodicity of the chain, we define|N + 1, ± ≡ |1, ±.

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20.3.1 Show that

ˆ

H1|n, ± = A(|n − 1, ± + |n + 1, ±) + |ψ n  ,

where|ψ n  is orthogonal to the subspace E1.

Without giving the complete form of |ψ n , give an example of one of its

components, and give the energy of the eigenspace of ˆH0to which|ψ n  belongs.

20.3.2 Consider the circular permutation operator ˆT , and its adjoint ˆ T † ,

defined by

ˆ

T |σ1, σ2, · · · , σ N  = |σ N , σ1, · · · , σ N−1 

ˆ

T † |σ1, σ2, · · · , σ N  = |σ2, σ3, · · · , σ N , σ1

Write the action of ˆT and ˆ T † on the states|n, ±.

20.3.3 Check that, in the subspace E1, ˆ H1 and A( ˆ T + ˆ T †) have the same

matrix elements

20.3.4 Show that the eigenvalues λ k of ˆT are the N -th roots of unity (we recall that N is assumed to be even):

λ k = e−iq k q k =−π + 2kπ

N k = 0, · · · , N − 1

20.3.5 We seek, inE1, the 2N eigenvectors |q k , ± of ˆ T , each corresponding

to an eigenvalue λ k Each|q k , ± is written

|q k , ± =

n

(a) Write a recursion relation between the coefficients c n

(b) Show that

c n (k) = √1

Ne

is a solution of this recursion relation

(c) Show that the states |q k , ± defined using (20.1) and (20.2) are

ortho-normal

(d) Show that the vectors|q k , ± are also eigenvectors of ˆ T †and ˆT + ˆ T †, and

give the corresponding eigenvalues

(e) Calculate the scalar productn, |q k ,    (,  =±) and write the

expan-sion of the states|n, ± in the basis |q k , ±.

20.3.6 We treat the Hamiltonian ˆH1 of Sect 2 as a perturbation to ˆH0.

We limit ourselves to the first excited level of ˆH0, and we want to calcu-late how the perturbation lifts the degeneracy of this level We recall that,

in the degenerate case, first order perturbation theory consists in diagonaliz-ing the restriction of the perturbdiagonaliz-ing Hamiltonian in the degenerate subspace

of the dominant term ˆH

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206 20 Magnetic Excitons

(a) Explain why the results of questions 3.3 and 3.5 above allow one to solve this problem

(b) In first order perturbation theory, give the new energy levels which arise from the first excited state of ˆH0, and the corresponding eigenstates (c) Draw qualitatively the energies E(q k ) in terms of the variable q k which

can be treated as a continuous variable, q k ∈ [−π, +π[, if N is very large.

1 What is the degeneracy of each new energy level?

20.4 Vibrations of the Chain: Excitons

We now study the time evolution of the spin chain

20.4.1 Suppose that at time t = 0, the system is in the state

|Ψ(0) =

=±

N−1

k=0

ϕ  k |q k ,   with 

=±

N−1

k=0

|ϕ 

k |2= 1 Setting ω = 2A/¯ h, write the state |Ψ(t) at a later time t.

20.4.2 We assume that the initial state is |Ψ(0) = |q k , + .

(a) Write the probability amplitude α n (t) and the probability P n (t) of finding

at time t the n-th spin pointing upwards, i.e σ n = +1 and σ m = 0 for

m = n Show that P n (t) is the same for all sites of the chain.

(b) The molecules of the chain are located at x n = na, where a is the lattice spacing Show that the probability amplitude α n (t) is equal to the value

at x = x n of a monochromatic plane wave

Ψ k (x, t) = Ce i(p(q)x −E(q)t)/¯h ,

where C is a constant, q = q k , and x is the abscissa along the chain Express p(q) in terms of q.

(c) Show that Ψ k (x, t) is an eigenstate of the momentum operator ˆ p x = (¯h/i)∂/∂x along the chain.

Show that the value of p(q) ensures the periodicity of Ψ k (x, t), i.e Ψ k (x +

L, t) = Ψ k (x, t), where L = N a is the length of the chain.

(d) Show that, for |q k |  1, Ψ k (x, t) satisfies a Schr¨odinger equation for a

particle of negative mass m, placed in a constant potential; give the value

of m.

20.4.3 In a more complete analysis, one can associate quasi-particles to the

magnetic excitations of the chain These quasi-particles, which we call

“mag-netic excitons”, have an energy E(q k ) and a momentum p(q k)

At very low temperatures, T ≈ 1.4 K, the chain is in the ground state

of ˆH0 If low energy neutrons collide with it, they can create excitons whose

energy and momentum can be determined by measuring the recoil of the

neutrons The experimental result for E(q) as a function of q ∈ [−π, 0] is

given in Fig 20.1

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Fig 20.1 Experimental measurement of the excitation energy E(q) as a function

of q between −π and 0 The energy scale is in meV (10 −3eV)

(a) Deduce from that data approximate values for D and A.

(b) What do you think of the approximation D  A and of the comparison

between theory and experiment? How could one improve the agreement between theory and experiment?

(c) Is it justified to assume that the chain is in its ground state when it

is at thermal equilibrium at 1.4 K? We recall the Boltzmann factor:

N (E2)/N (E1) = exp[−(E2− E1)/kT ], with k = 8.6 × 10 −5 eV K−1.

20.4.4 Consider, at time t = 0, the state

|Ψ(0) =

N−1

k=0

ϕ k |q k , +  with

N−1

k=0

|ϕ k |2= 1.

We assume that N  1, that the coefficients ϕ k have significant values only

in a close vicinity of some value k = k0, or, equivalently, q ≈ q0, and that, to

a good approximation, in this vicinity,

E(q) = E(q0) + (q − q0)u0, u0=dE

dq





q=q0

.

Show that the probability P n (t) of finding σ n = +1 at time t is the same as the probability P n  (t  ) of finding σ n  = +1 at another time t  whose value will

be expressed in terms of t and of the distance between the sites n and n  .

Interpret the result as the propagation of a spin excitation wave along the chain Calculate the propagation velocity of this wave and give its numerical

value for a = 0.7 nm and q0=−π/2.

20.4.5 We now assume that the initial state is|Ψ(0) = |n = 1, +.

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208 20 Magnetic Excitons

(a) Write the probability P m (t) of finding σ m = +1 at a later time t? (b) Calculate the probabilities P1(t) and P2(t), in the case N = 2, and

inter-pret the result

(c) Calculate P1(t) in the case N = 8 Is the evolution of P1(t) periodic? (d) For N  1, one can convert the above sums into integrals The prob-abilities are then P m (t) ≈ |J m−1 (ωt) |2 where the J n (x) are the Bessel

functions These functions satisfy

|J n (x) |2= 1 and J n = (−) n J −n .

For x  1 we have J n (x) ≈ 2

πx cos(x − nπ/2 − π/4) if x > 2|n|/π, and

J n (x) ≈ 0 if x < 2|n|/π.

Which sites are appreciably reached by the probability wave at a time t such that ωt  1?

(e) Interpret the result as the propagation along the chain of a probability amplitude (or wave) Calculate the propagation velocity and compare it with the result obtained in question 4.4)

20.5 Solutions

Section 20.1: The Molecule CsFeBr 3

20.1.1 The results are: ˆJ2: 2¯h2, ˆ J z : m¯ h ; m = 1, 0, −1.

20.1.2 One has:

J+|1 = 0

J+|0 = ¯h √

2|1

J+| − 1 = ¯h √2|0

J − |1 = ¯h √

2|0

J − |0 = ¯h √

2| − 1

J − | − 1 = 0

20.1.3 The eigenstates are the states |σ The state |0 corresponds to the eigenvalue E = 0, whereas |+ and |−, which are degenerate, correspond to

E = D.

Section 20.2: Spin–Spin Interactions in a Chain of Molecules 20.2.1 It is straightforward to see that

ˆ

H01, σ2· · · σ N  = D

N



n=1

(σ n)21· · · σ N  ,

the corresponding eigenvalue being E = D

σ2

n

20.2.2 The ground state of ˆH0 corresponds to all the σ n equal to zero, so

that E = 0 This ground state is non-degenerate.

20.2.3 The first excited state corresponds to all the σ’s being zero except

one: σ nequal to±1 The energy is D, and the degeneracy 2N, since there are

N possible choices of the non-vanishing σ n, and two values±1 of σ n

20.2.4 J ± = J x ± iJ y A direct calculation leads to the result.

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Section 20.3: Energy Levels of the Chain

20.3.1 The action of the perturbing Hamiltonian on the basis states is,

set-ting  = ±:

ˆ

H1|n,  = A (|n − 1,  + |n + 1, )

n  =n

(|0, · · · 0, σ n = , 0 · · · 0, σ n  =−1, σ n +1= +1, 0 · · · 0

+|0 · · · 0, σ n = , 0 · · · 0, σ n  = +1, σ n +1=−1, 0 · · · 0)

The vector|ψ = |σ1= 1, σ2=−1, 0 · · · 0, σ n = , 0 · · · 0 belongs to this latter

set; it is an eigenvector of ˆH0 with energy 3D.

20.3.2 The definition of ˆT , ˆ T † and|n, ± implies:

ˆ

T |n, ± = |n + 1, ± ; Tˆ† |n, ± = |n − 1, ±

20.3.3 We therefore obtain

A( ˆ T + ˆ T †)|n, ± = A(|n − 1, ± + |n + 1, ±)

Since

ˆ

H1|n, ± = A(|n − 1, ± + |n + 1, ±) + |ψ n  where n  , ±|ψ n  = 0 ,

ˆ

H1 and A( ˆ T + ˆ T †) obviously have the same matrix elements in the subspace

E1.

20.3.4 Since ˆT N = ˆI, an eigenvalue λ k satisfies λ N k = 1, which proves that

each eigenvalue is an N -th root of unity Conversely, we will see in the following that each N -th root of unity is an eigenvalue.

20.3.5 (a) The corresponding eigenvectors satisfy

|q k , ± =

n

c n |n, ± Tˆ|q k , ± = λ k |q k , ±

therefore one has



n

c n |n + 1, ± = λ k



n

c n |n, ±

Hence the recursion relation and its solution are

λ k c n = c n−1 c n = 1

λ n−1 k

c1= eiq k (n −1) c

1 .

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210 20 Magnetic Excitons

(b) The normalization condition

n |c n |2= 1 gives N |c1|2= 1 If we choose

c1= eiq k / √

N , the eigenvectors are of unit norm and we recover the solution

given in the text of the problem

(c) The scalar product of|q k ,   and |q k  ,    is easily calculated:

q k  ,   |q k ,   = δ ,  1

N



n

e2iπn(k −k  )/N

= δ ,  δ k,k 

(d) The vectors |q k , ± are eigenvectors of ˆ T † with the complex conjugate

eigenvalues λ ∗

k Therefore they are also eigenvectors of ˆT + ˆ T †with the

eigen-value λ k + λ ∗

k = 2 cos q k=−2 cos(2kπ/N).

(e) From the definition of the vectors, we have

n, |q k ,    = √1

Ne

iq k n δ  

and (directly or by using the closure relation)

|n, ± = √1

N

N−1

k=0

e−iq k n |q k , ±

20.3.6 The restriction of ˆH1 to the subspace E1 is identical to A( ˆ T + ˆ T †)

(question 3.3) InE1, the operator A( ˆ T + ˆ T †) is diagonal in the basis|q k , ±.

Therefore the restriction of ˆH1is also diagonal in that basis The energy levels are

E(q k ) = D + 2A cos(q k ) , (20.3) corresponding to the states|q k , ± As far as degeneracies are concerned, there

is a twofold degeneracy for all levels (the spin value may be +1 or −1) In addition, for all levels except q = −π and q = 0, there is a degeneracy q k ↔

−q k (symmetry of the cosine) Therefore, in general, the degeneracy is 4

Section 20.4: Vibrations of the Chain: Excitons

20.4.1 At time t the state of the chain is (cf (20.3)):

|Ψ(t) = e −iDt/¯h





k

ϕ  ke−iωt cos q k |q k ,  

20.4.2 We now consider an initial state|q k , ±, evolving as e −iE(q)t/¯h |q k , ±.

(a) We therefore obtain an amplitude

α n (t) = √1

Ne

i(q k n−E(q k )t/¯ h)

and a probability P n (t) = |α n |2= 1

N, which is the same on each site

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(b) In the expression

α n (t) = √1

Ne

i(q k x n /a−E(q k )t/¯ h) ,

we see that α n (t) is the value at x = x n of the function Ψ k (x, t) =

1

√ N exp[i(px − Et)/¯h] with E(q) = D + ¯hω cos q and p(q) = ¯hq/a.

(c) The function Ψ k (x) is an eigenstate of ˆ p x with the eigenvalue ¯hq k /a Since N is even, we obtain:

eiq k L/a= eiNq k = e2πik = 1 , which proves the periodicity of Ψ k

(d) For|q k |  1, cos q k= 1− q2

k /2 Therefore E = E0+ p2/2m with

E0= D + 2A and m = − ¯h

2

2Aa2 =− ωa¯h2 .

Ψ k then satisfies the wave equation

h ∂ψ

∂t =¯h

2

2m

2ψ

∂x2 + E0ψ ,

which is a Schr¨odinger equation for a particle of negative mass (in solid state physics, this corresponds to the propagation of holes and in field theory, to the propagation of anti-particles)

20.4.3 (a) With the data of the figure which resemble grosso modo the

E(q) drawn in Fig 20.2, one finds D + 2A ∼ 3.2 × 10 −3 eV, and D − 2A ∼ 0.4 × 10 −3 eV Therefore:

D ∼ 1.8 × 10 −3eV A ∼ 0.7 × 10 −3 eV

(b) The approximation D  A is poor The theory is only meaningful to order (A/D)2∼ 10% Second order perturbation theory is certainly necessary

to account quantitatively for the experimental curve which has a steeper shape

than a sinusoid in the vicinity of q = −π.

(c) For T = 1.4 K, kT ∼ 1.2 × 10 −4 eV, exp(−(D − 2A)/kT ) ∼ 0.04 To a

few % , the system is in its ground state

20.4.4 Approximating E(q) = E(q0) + (q − q0)u0 in the vicinity of q0, we obtain

α n (t) = √1

Ne

i(q0n−ω0t)

k

ϕ kei(q k −q0 )(n −u0 t/¯ h)

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212 20 Magnetic Excitons

Fig 20.2 Energy levels

Since the global phase factor does not contribute to the probability, one has

P n (t) = P n  (t ) with

t  = t + (n  − n)¯h

u0 .

This corresponds to the propagation of a wave along the chain, with a group velocity

vg= u0a

¯

h =

a

¯

h

dE dq





q=q0

=− 2a A

¯

h sin q0 . For q0 = −π/2 and a = 0.7 nm, we find vg ∼ 1500 ms −1 One can also

evaluate u0 ∼ 1.2 meV directly on the experimental curve, which leads to

vg∼ 1300 ms −1.

20.4.5 If|Ψ(0) = |n = 1, +, then ϕ+

k = e−iq k / √

N and ϕ −

k = 0

(a) The probability is P m (t) = |m, +|Ψ(t)|2, where

m, +|Ψ(t) = e−iDt/¯h

N



k

eiq k (m −1)e−iωt cos q k

(b) N=2:

There are two possible values for q k : q0 = −π and q1 = 0 This leads to

P1(t) = cos2ωt, P2(t) = sin2ωt These are the usual oscillations of a

two-state system, such as the inversion of the ammonia molecule

(c) N=8:

cos(q k) −1 − √1

2

The probability P1 of finding the excitation on the initial site is

P1(t) = 1

4

 cos2(ωt/2) + cos(ωt/ √

2)

2

The system is no longer periodic in time There cannot exist t = 0 for which

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