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Use separation of variables in Cartesian coordinates to solve infinite cubical well

V(x,y,z)=0if x,y,z are all between 0 to a;

V(x,y,z)=Otherwise

a) Find the stationary states and the corresponding energies

b) Call the distinct energies E1,E2,E3,..in the order of increasing energy. Findlocalid="1658127758806" E1,E2,E3,E4,E5,E6determine their degeneracies (that is, the number of different states that share the same energy). Comment: In one dimension degenerate bound states do not occur but in three dimensions they are very common.

c) What is the degeneracy of E14 and why is this case interesting?

Short Answer

Expert verified

(a) Ψ(x,y,z)=(2a)32sin(nxπaX)sin(nyπay)sin(nzπaz)E(x,y,z)=π2h22ma2(nx2+ny2+nz2)nx,ny,nz=1,2,3,.......

(b) Distinct energies calculated in the step 3.

(c) E14=4

Step by step solution

01

Define the Schrödinger equation

A differential equation describes matter in quantum mechanics in terms of the wave-like properties of particles in a field. Its answer is related to a particle's probability density in space and time.

02

Determine the corresponding energies

-h22m(2Ψx2+2Ψy2+2Ψz2)=EΨ

Separable solutions:Ψ(x,y,z)=X(x)Y(y)Z(z)

Put this in and divide by XYZ

role="math" localid="1658128747853" -h22m2Ψ+VΨ=EΨ1Xd2xdx2+1Yd2Ydy2+1Zd2Zdz2=-2mh2E

The three terms on the left are functions of x,y,z, so each must be a constant, call the separation constants Kx2,Ky2,Kz2

d2Xdx2=-Kx2X;d2Ydy2=-Ky2Y;d2Zdz2=-Ky2ZX(x)=Axsinkxx+BxcoskxxY(y)=AysinkyY+BycoskyYZ(z)=AzsinkzZ+BzcoskzZX(0)=0,Bx=0;Y(0)=0,By=0Z(0)=0,Bz=0X(a)=0sin(kxa)=0kxa=nττkx=nxττa,ky=nyττa,kz=nzττaψ(x,y,z)=AxAyAzsin(nxττaX)sin(nyττaY)sin(nzττaZ)Ax=AY=Az=2aψ(x,y,z)=(2a)32sin(nxττaX)sin(nyττaY)sin(nzττaZ)E(x,y,z)=π2h22a(nx2+ny2+nz2)

03

Determine the distinct energies

d=1;E1=E111=3π2h22ma2d=2;E2=E211=E121=E112=6π2h22ma2d=3;E3=E221=E212=E122=9π2h22ma2d=3;E4=E311=E131=E113=11π2h22ma2d=1;E5=E222=12π2h22ma2d=1;E6=E123=E231=E312=E132=E213=E321=14π2h22ma2

04

Step 4:Determine the degeneracy

After calculatingE7,E8,.....,E13we find that:

E14=E333=E115, so the degeneracy is 4.

This is called "accidental degeneracy" since (3,3,3)and (1,1,5)conspired to have the same energy eigenvalue 27.

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Most popular questions from this chapter

Find the matrix representingSxfor a particle of spin3/2 (using, as

always, the basis of eigenstates ofSz). Solve the characteristic equation to

determine the eigenvalues ofSx.

Determine the commutator of S2withSZ(1)(whereSS(1)+S(2)) Generalize your result to show that

[S2,S1]=2Ih(S1×S2)

Comment: Because Sz(1)does not commute with S2, we cannot hope to find states that are simultaneous eigenvectors of both. In order to form eigenstates ofS2weneed linear combinations of eigenstates ofSz(1). This is precisely what the Clebsch-Gordan coefficients (in Equation 4.185) do for us, On the other hand, it follows by obvious inference from Equation 4.187that the sumrole="math" localid="1655980965321" S(1)+S(2)does commute withdata-custom-editor="chemistry" S2, which is a special case of something we already knew (see Equation 4.103).

What is the probability that an electron in the ground state of hydrogen will be found inside the nucleus?

  1. First calculate the exact answer, assuming the wave function is correct all the way down tor=0. Let b be the radius of the nucleus.
  2. Expand your result as a power series in the small numbera=2bla, and show that the lowest-order term is the cubic:P(4l3)(bla)3. This should be a suitable approximation, provided thatba(which it is).
  3. Alternatively, we might assume thatψ(r)is essentially constant over the (tiny) volume of the nucleus, so thatP(4l3)πb3lψ(0)l2.Check that you get the same answer this way.
  4. Useb10-15manda05×10-10mto get a numerical estimate forP. Roughly speaking, this represents the fraction of its time that the electron spends inside the nucleus:"

A hydrogenic atom consists of a single electron orbiting a nucleus with Z protons. (Z=1 would be hydrogen itself,Z=2is ionized helium ,Z=3is doubly ionized lithium, and so on.) Determine the Bohr energies En(Z), the binding energyE1(Z), the Bohr radiusa(Z), and the Rydberg constant R(Z)for a hydrogenic atom. (Express your answers as appropriate multiples of the hydrogen values.) Where in the electromagnetic spectrum would the Lyman series fall, for Z=2and Z=3? Hint: There’s nothing much to calculate here— in the potential (Equation 4.52) Ze2, so all you have to do is make the same substitution in all the final results.

V(r)=-e24πo0˙1r (4.52).

The (time-independent) momentum space wave function in three dimensions is defined by the natural generalization of Equation 3.54:

Φ(p,t)=12πhe-ipx/hψ(x,t)dx(3.54).ϕ(p)1(2πh)3/2e-i(p.r)Ihψ(r)d3r.(4.223).

(a)Find the momentum space wave function for the ground state of hydrogen (Equation 4.80). Hint: Use spherical coordinates, setting the polar axis along the direction of p. Do the θ integral first. Answer:

ψ100(r,θ,ϕ)=1πa3e-r/a(4.80).ϕ(p)=1π(2ah)3/21[1+ap/h2]2.(4.224).

(b) Check that Φ(p)is normalized.

(c) Use Φ(p)to calculate <p2>, in the ground state of hydrogen.

(d) What is the expectation value of the kinetic energy in this state? Express your answer as a multiple of E1, and check that it is consistent with the virial theorem (Equation 4.218).

<T>=-En;<V>=2En(4.218).

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