16.11.1: Solutions
( \newcommand{\kernel}{\mathrm{null}\,}\)
These answers are intended to reassure that you have got the problems right. They are not model solutions, and would be unacceptably terse as examination solutions.
1: Perturbation and Matrix Elements
For integer n:
1√acos(2n+1)πx2a;1√asin2nπx2a
For perturbation theory va should be much smaller than the difference between energy levels of different n:
va<<(2n+1)π2ℏ28ma2
First order energy shift: ⟨n|vx|n⟩=0.
Matrix elements, by symmetry, integer n,m: ⟨2m|vx|2n⟩=⟨2m+1|vx|2n+1⟩=0
For n odd, m even:
Vnm=4avπ2∫π/2−π/2ycos(ny)sin(my)dy e.g. V12=32va9π2
⟨267|vx|387⟩=⟨m|vx|m+738⟩=0
2: Completeness and Orthonormality in Vectors
Consider a unit vector a=(1,1,3)/√11. What are its components (dot products) in the following ‘basis sets’ ui:
a) 1/√11,1/√11,3/√11: complete, orthogonal, normalised
b) (√3+1)/2√11,(1−√3)/2√11: incomplete, orthogonal, normalised
c) (√3+3)/2√11,(√3+3)/2√11,1/√11: complete, non-orthogonal, normalised
d) (√3+3)/2√11,(1−3√3)/2√11,1/√11: complete, orthogonal, normalised
e) 0,7/√11,−6/√11: complete, orthogonal, unnormalised
f) (3−√3)/2√11,(1+3√3)/2√11,1/√11,0. overcomplete, non-orthogonal, unnormalised
g) √2/√11,3/√11: incomplete, orthogonal, normalised
h) (1+√3)/2√11,(1−√3)/2√11,√2/√11: incomplete, non-orthogonal, normalised Complete, orthogonal and normalised iff for any a:
∑i|ui⋅a|2=1 and ui⋅uj=δij
The Fourier series is orthogonal and tends to completeness as k→∞. Atomic orbitals centerd on different sites are not orthogonal and may become overcomplete. Thus Fourier series have an advantage in completeness. However, the bonding orbitals in H2 are more similar to the atomic ones, and a basis set of just two 1s wavefunctions gives as good a description of the bonding as could hundreds of Fourier components.
3: One electron atoms
a) ⟨Φnl0|vˆlz|Φnl0⟩=0;;⟨Φ211|vˆlz|Φ211⟩=vℏ;;⟨Φ21−1|vˆlz|Φ21−1⟩=−vℏ
b) ⟨Φ100|vr2|Φ100⟩=3v(a0/Z)2;⟨Φ200|vr2|Φ200⟩=42v(a0/Z)2;⟨Φ210|vr2|Φ210⟩=30v(a0/Z)2⟨Φ21±1|vr2|Φ21±1⟩=30v(a0/Z)2
c) ⟨Φ100|vr|Φ100⟩=1⋅5v(a0/Z);⟨Φ200|vr|Φ200⟩=6v(a0/Z);⟨Φ210|vr|Φ210⟩=2⋅5v(a0/Z)⟨Φ21±1|vr|Φ21±1⟩=2⋅5v(a0/Z)
d) ⟨Φ100|ve−2r/a0|Φ100⟩=v(ZZ+1)3;⟨Φ200|ve−2r/a0|Φ200⟩=vZ3[(1Z+2)3+(3Z2(Z+2)5+3Z(Z+2)4];⟨Φ21m|ve−2r/a0|Φ21m⟩=v2(zz+2)5
e) ⟨Φ100|ve−Zr/a0|Φ100⟩=8v27;⟨Φ200|ve−Zr/a0|Φ200⟩=v32;⟨Φ21m|ve−Zr/a0|Φ21m⟩=v64
Notice that all off-diagonal terms with the same n are zero: none of these perturbations mix the eigenstates. (a) actually commutes with the Hamiltonian, so doesn’t mix n=1 with n=2 states, in this case the energy shifts are exact for any v. (b-e) mix states of n=1 and n=2, and so perturbation is only correct when the matrix element is much less than the energy difference between the n=1 and n=2 states (0.75 Z2 Ryd.).
4: Commutation
−iℏ,0,0,iℏz,0,iℏˆpz,iℏˆlz
5: Spin-Orbit Coupling
ˆj2=(ˆl+ˆs)2=ˆl2+2ˆl⋅ˆs+ˆs2⇒ˆl⋅ˆs=12[ˆj2−ˆl2−ˆs2]
For 1s and 2s, ΔE=0
For 2p, fourfold degenerate, J=±32,ΔE=η/2
For 2p, twofold degenerate, J=±12,ΔE=−η
First order because we assume the perturbed wavefunctions are the same as the hydrogen ones. Degeneracy is only partly lifted because there is still symmetry with respect to rotating the atom. Note that four levels are raised by η/2 while two are lowered by η: the ‘average energy’ of a 2p state in unaffected, though in fact each atom will be in one state or the other, so this is not a conservation law.
6: Degenerate Perturbation
Other orthogonal state: cos(θ+π2)|α1⟩+sin(θ+π2)|α2⟩.
⟨α2|ˆV|α1⟩=V1 since operator must be Hermitian. Eigenvalues of the matrix are V0±V1, so splitting between levels is 2V1. Eigenstates correspond to θ=±π/4.
Initial state is |α1⟩. When ˆV is applied it collapses onto |α(±π/4)⟩. For both of these states |⟨α(±π/4)|α2⟩|2=12, thus the probability of measuring |α2⟩ when the perturbation is removed is 12.
Time dependent perturbation theory would be inappropriate because the perturbation is larger than the energy difference between the unperturbed states (which is zero).
7: Good quantum numbers in hydrogen
b), e) and j) are good sets. a) is not good since Lz and Lx do not commute. d) is not good since x does not commute with the other operators. c), g), h), i) and j) do not give different labels to |200↑⟩ and |210↑⟩. f) does not give different labels to |211↓⟩ and |210↑⟩.
8: Periodic perturbation
Energy of ϕ± is ℏ2k2/2m and they are eigenfunctions of ˆH0.
Momentum of ϕ± is ℏk and they are eigenfunctions of ˆp.
⟨ϕ+|ˆV(x)|ϕ+⟩=⟨ϕ−|ˆV(x)|ϕ−⟩=0
⟨ϕ+|ˆV(x)|ϕ−⟩=⟨ϕ−|ˆV(x)|ϕ+⟩=0 unless 2Lk=Nπ
Think about what this means - to first order, a free electron travelling through a periodic potential (e.g. a crystal) is not affected by that potential! This is why the free electron theory of metals works reasonably well.
If 2Lk=Nπ then: ⟨ϕ+|ˆV(x)|ϕ−⟩=⟨ϕ−|ˆV(x)|ϕ+⟩=V0/2
Appropriate states are (ϕ+±ϕ−)/√2, which are still eigenfunctions of H0 but not of ˆp.
This analysis is similar to the opening of a band gap by a periodic potential in solid state band theory of a one dimensional crystal.
The non-zero matrix element from combining terms on either side of |k|=Nπ/2L is
∫L0 exp[i(Nπ+δ)x/2L]vocos(2kx) exp[i(Nπ−δ)x/2L]dx=L/2
Thus the second order energy shift of the state at |k|=Nπ/2L−δ is:
ΔE=−(voL/2)2ℏ22Nπδ/8mL2=−mv20Nℏ2πδ
i.e. its energy is reduced. Even second order perturbation breaks down as δ→0 (because the unperturbed states are closer together in energy than the size of the perturbation), but we do know the exact limit to which the energy shift should tend from the degenerate result above.
9: Stark Effect
There are 81 elements, of which 73 are zero. Of the remaining eight, there are four equal pairs ⟨300|z|310⟩, ⟨320|z|310⟩ and ⟨32±1|z|31±1⟩, and in fact only two are distinct since ⟨320|z|310⟩=⟨32±1|z|31±1⟩.
Defining a=⟨300|z|310⟩ and b=⟨320|z|310⟩, we can block diagonalise the matrix and find the eigenvalues:
−√(a2+b2),0,√(a2+b2),b,−b,b,−b,0,0.
10: Neutral kaons
CP|K0⟩=|¯K0⟩;CP|¯K0⟩=|K0⟩
Consider a general state |ϕ⟩=a0|K0⟩+b0|¯K0⟩
The total intensity is proportional to ⟨ϕ|ϕ⟩=|a0|2+|b0|2, of which |a0|2 are K0s. And
⟨ϕ|12(ˆS+1)|ϕ⟩=|a0|2
Similarly, the intensity of ¯K0 is |b0|2 and comes from the expectation value of 12(1−ˆS)
If we assume K0 intensity IK0(t)=|a0(t)|2, then.
|a0(t)|2=⟨12(ˆS+1)⟩=14|a0(0)|2[e−t/τ1+e−t/τ2+2e−t/2τ1e−t/2τ2cos(m12t)]
⟨ˆS⟩=|a0(0)|2e−t/2τ1e−t/2τ2cos(m12t)
⟨ˆS2⟩=12|a0(0)|2(e−t/τ1+e−t/τ2)
⟨12(^CP+1)⟩=12|a0(0)|2e−t/τ1
⟨^CP⟩=12|a0(0)|2(e−t/τ1−e−t/τ2)
Leaving the matter, the appropriate collapsed eigenstates are |K0⟩ and |¯K0⟩
The final kaon intensity is a quarter of the initial intensity. Had the matter not intervened, the final kaon intensity would have been half of the initial intensity.
11: Variational principle
a)a2=√π2−612mωℏ;⟨ˆH0⟩=0.568ℏω
b)a2=√352ℏmω;⟨ˆH0⟩=0.598ℏω
c)α=mω2ℏ;⟨ˆH0⟩=0.5ℏω
d)a2=√15πℏmω;⟨ˆH0⟩=0.548ℏω
e)a2=√2π2−36mωℏ;⟨ˆH0⟩=1.607ℏω
12: Degenerate Perturbation
Eigenstates: [sinπxLcosπy2L±sinπyLcosπx2L]/L
Energy shifts = ±102481π4vL2
13: Properties of Legendre Polynomials
∫π0Pl(cosθ)Pm(cosθ)dθ=δml22l+1
Pl(1)=1 and P0(0)=1, P2(0)=0, P3(0)=12, P4(0)=0.
For the dipole, V=eEz etc. Δl=±1 (θ integral), Δms=0 (spin integral), Δml=±1,0 (ϕ integral)
For the quadrupole, V=eExy etc. Δl=±2,0 (θ integral), Δms=0 (spin integral), Δml=±2, ±1,0 (ϕ integral)
14: Abstract Operators
ˆQ=(1000)
The eigenvectors are just |p⟩=[10] and |n⟩=[01], the eigenvalues are 1 and -1
ˆT1=(0110)
eigenstates of ˆT1 are [√12,√12] and [√12,−√12] both with charge expectation values of 12
15: Density of states - Born Approximation
States between E and E+dE: mkL32ℏ2π2dE
States between E and E+dE and angle between θ and θ+dθ: mkL34ℏ2π2sinθdθdE
16: Impact Parameters
Impact parameter for 1eV p-electron: 2.75∘A
17: Partial Waves
According to Levinson’s Theorem there are two bound states, both with l=0.
There will be a minimum in the cross section when δ0=2π, E=1eV.
There are maxima in the cross section at δ0=3π/2: E=1.78eV and when δ1=π/2: E=10eV. However, the δ1=π/2 maximum is coincident with the maxima from the other l-components, and thus this is the energy with strongest scattering. The ratio of scattering strengths is 35/10:1/1.78≈6.2
At high energy, the scattering falls as σmax/2E, since the average value of sin2δ≈1/2.
18: Atomic Scattering
dσdθ=m2e44π2ϵ20ℏ4[2ksinθ2]−4[F(χ)−Z]2=e464π2ϵ20sin−4θ21m2v4[F(χ)−Z]2
19: Coulomb Scattering
No Planck constant - the expression is the same as the classical Rutherford cross section.
20: Hydrogen Scattering
Redefine axes for integral over all space such that polar axis is along χ. Use standard formula for ∫re−ardr with complex a.
21: Centre of mass coordinates
With M=m1+m2 and μ=(m1m2)/(m1+m2) and total energy E=Er+ER, the equations are:
−ℏ22μ∂2∂r2Φ+V(r)Φ=ErΦ
−ℏ22M∂2∂R2Φ=ERΦ
22: Imaginary Potentials
Φ=AeV1t/ℏeikx−iwt+BeV1t/ℏe−ikx−iwt
Is the general solution, so that ⟨Φ|Φ⟩=(A20+B20)e2V1t/ℏ. The probability current density is then :
(ℏkm)e2V1t/ℏ(B20−A20)
Particles are being created. If V1 were negative it would represent particles decaying.
23: Electron-electron scattering
(a)dσdθ=(e28πϵ02E)2sin−4θ2
(b)dσdθ=(e28πϵ02E)212(sin−2θ2−cos−2θ2)2
(c)dσdθ=(e28πϵ02E)212([sin−2θ2−cos−2θ2]2+sin−4θ2)
24: Bell’s Theory
(a) 14
(b) cos2(θA)cos2(θB)
(c) 12cos2(θA−θB)
(d) 14
(e) 12cos212(θA−θB)
The factor of two arises because opposite-polarised photons (x and y) are at 90∘ while opposite spins Sz=±12 are at 180∘ to one another.
Hidden variables methods would give the same result for (a), (b) and (d), but will incorrectly predict for (c) 14cos2(θA−θB) and for (e) 14cos212(θA−θB)
The probability averaged over all θA and θB is 14 in every case.
25: Kronig-Penney
When l=b, the equation becomes simply cosk1b=coskb, whence the energy is E=ℏ2k2/2m.
When b=0 we have cosk2l=coskl. For E>V0 this is just the free electron again. For E<V0, k2 is imaginary, iκ2 say, the equation becomes coshκ2l=coskl which has no solution except the trivial l=0.
The first two cases are simply free electrons, the final non solution shows that an electron must have at least the potential energy of the region where it is found.
26: Hydrogen Molecular Ion
The ground state is simply one hydrogen atom and one bare proton. Since there is a choice for which proton has the electron, it is doubly degenerate with energy E0. The wavefunction is simply the 1s orbital in hydrogen. Refer to these states as |1⟩ and |2⟩.
The integrals are the electron wavefunction acted on by the electric field of the other proton, premultiplied either by itself or the equivalent wavefunction on the other ion. Each increases towards infinity at R=0 and drops to zero as R →∞. V12 is larger.
The energies of the perturbed states are:
E0+V11±V12
The electron will fall into the lower energy state E0+V11−V12. This will produce a force between the atoms of
dEdR=dV11dR−dV12dR
since dV12dR<dV11dR, this force is attractive. (Check it using MAPLE)
The protons do not collide because of their mutual Coulombic repulsion.
The approximation comes in not including n=2 basis functions in the wavefunction. It will break down when V12≈34RH, where RH is the Rydberg constant.
Some Integrals
∫a−a(Any odd function)dx=0
∫a0xcos2(nπx2a)dx=a24[1−4n2π2] n odd ;∫a0xsin2(nπx2a)dx=a24[1+4n2π2] n odd
∫a0xsin2(nπx2a)dx=∫a0xcos2(nπx2a)dx=a24 n even
∫π/2−π/2xcos2xsinxdx=49
∫∞0xnexp(−ax)dx=n!a−(n+1)
∫L0cos2(πx/L)dx∫L0sin2(πx/L)dx=L/2
∫π/a−π/ax2sin2naxdx=π(2n2π2−3)6n2a3;∫π/a−π/ax2cos2naxdx=π(2n2π2+3)6n2a3
∫a−aa4−2a2x2+x4dx=1615a5
∫∞−∞x2exp(−x2/σ2)dx=σ3√π2
∫∞−∞exp(−x2/σ2)dx=σ√π
∫a0x2(x−a)2dx=a530
∫π/2−π/2∞∑n=1cos2nxn2dx=π316
∫∞−∞d3x∫∞−∞d3yρ(x)exp(−ik.y)|x−y|=∫∞−∞d3x∫∞−∞d3zρ(x)exp−ik.(x+z)|z|=4πk2∫∞−∞d3xρ(x)exp−ik.x
∫∞0xexp(−2x/a)cos(χx)=a2(χ2a2−4)(χ2a2+4)2