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Quantum Angular Momentum and H-Atom


Introduction

Quantum angular momentum is a fundamental concept in quantum mechanics. It describes the rotational properties of quantum systems and plays an important role in atomic structure. The hydrogen atom provides an important application of angular momentum theory through the Schrödinger equation.

1. Orbital Angular Momentum

Orbital angular momentum is defined as:

L = r × p

Using the momentum operator p = −iℏ∇:

L = −iℏ(r × ∇)

The angular momentum components satisfy the commutation relations:

[Lₓ, Lᵧ] = iℏL_z

[Lᵧ, L_z] = iℏLₓ

[L_z, Lₓ] = iℏLᵧ

2. Angular Momentum Eigenvalues

The squared angular momentum and its z-component have eigenvalues:

L²|l,m⟩ = ℏ²l(l+1)|l,m⟩

L_z|l,m⟩ = mℏ|l,m⟩

Therefore, the magnitude of orbital angular momentum is:

|L| = ℏ√[l(l+1)]

For orbital angular momentum, l = 0, 1, 2, ... and m = −l, ..., 0, ..., +l.

3. Spherical Harmonics

Spherical harmonics, represented by Yₗᵐ(θ, φ), are the angular eigenfunctions of the angular momentum operators.

L²Yₗᵐ = ℏ²l(l+1)Yₗᵐ

L_zYₗᵐ = mℏYₗᵐ

They describe the angular dependence of atomic orbitals and are essential for solving the Schrödinger equation in spherical coordinates.

4. Hydrogen Atom Hamiltonian

The hydrogen atom consists of an electron and a proton interacting through the Coulomb potential. Its relative-motion Hamiltonian is:

H = −(ℏ²/2μ)∇² − e²/(4πε₀r)

Here, μ is the reduced mass:

μ = mₑmₚ/(mₑ + mₚ)

The stationary Schrödinger equation is:

Hψ = Eψ

Since the potential depends only on r, the equation can be separated into radial and angular parts.

5. Separation of Variables

The wavefunction is expressed as:

ψ(r,θ,φ) = R(r)Yₗᵐ(θ,φ)

The radial equation is:

−(ℏ²/2μ) d²u/dr² + V_eff(r)u = Eu

where u(r) = rR(r), and the effective potential is:

V_eff(r) = ℏ²l(l+1)/(2μr²) − e²/(4πε₀r)

The first term represents the centrifugal contribution, while the second is the attractive Coulomb potential.

6. Energy Eigenvalues

Solving the radial equation with the appropriate boundary conditions gives the hydrogen energy levels:

Eₙ = −13.6/n² eV

where n = 1, 2, 3, ... is the principal quantum number. This expression is an approximation that neglects fine structure and other small corrections.

7. Quantum Numbers and Degeneracy

The hydrogen atom is described by three spatial quantum numbers:

  • Principal quantum number: n = 1, 2, 3, ...
  • Orbital quantum number: l = 0, 1, ..., n − 1
  • Magnetic quantum number: m = −l, ..., +l

For a given principal quantum number, the number of spatial states is:

gₙ = n²

This degeneracy arises because the nonrelativistic hydrogen energy depends only on n.

8. Ground-State Wavefunction

For the ground state, n = 1, l = 0, and m = 0. The normalized wavefunction is:

ψ₁₀₀(r) = (1/√πa₀³)e^(−r/a₀)

Here, a₀ is the Bohr radius, approximately 0.529 Å for hydrogen when the proton's finite mass is neglected.

9. Spectral Transitions

When an electron transitions between energy levels, a photon is emitted or absorbed. Its energy is:

hν = |Eᵢ − E𝒻|

For electric-dipole transitions, the orbital selection rules are:

Δl = ±1

Δm = 0, ±1

Conclusion

Angular momentum provides the mathematical foundation for understanding atomic orbitals and rotational symmetry. Its application to the hydrogen atom explains the quantization of energy levels and the structure of atomic wavefunctions. These concepts form the basis for further studies of spin, fine structure, and atomic spectroscopy.

References

  • J. J. Sakurai and Jim Napolitano, Modern Quantum Mechanics.
  • R. Shankar, Principles of Quantum Mechanics.
  • David J. Griffiths and Darrell F. Schroeter, Introduction to Quantum Mechanics.

Gaussian Beams and Counter-Propagating Wave

The emphasis is on understanding where the equations come from rather than simply quoting the final result.


Superposition of Two Counter-Propagating Circularly Polarized Waves

Consider two equal-amplitude monochromatic plane waves propagating in opposite directions along the $z$-axis. Let their common electric-field amplitude be $E_0$, wave number be $k$, and angular frequency be $\omega$.

For electromagnetic waves in vacuum,

$$ \omega = ck. $$

The electric field of a plane wave can be written as

$$ \mathbf{E}(\mathbf r,t) = \operatorname{Re} \left\{ \mathbf E_0 e^{i(\mathbf k\cdot\mathbf r-\omega t)} \right\}. $$

(a) $+z$ wave is LCP and $-z$ wave is RCP

Wave propagating along $+z$

For the wave propagating in the $+z$ direction,

$$ \mathbf{k}_1=k\hat{\mathbf z}. $$

Take the left-circularly polarized electric field to be

$$ \mathbf E_1 = E_0 \operatorname{Re} \left[ (\hat{\mathbf x}-i\hat{\mathbf y}) e^{i(kz-\omega t)} \right]. $$

Taking the real part gives

$$ \boxed{ \mathbf E_1 = E_0 \left[ \hat{\mathbf x}\cos(kz-\omega t) + \hat{\mathbf y}\sin(kz-\omega t) \right] }. $$

Wave propagating along $-z$

For the second wave,

$$ \mathbf{k}_2=-k\hat{\mathbf z}. $$

For the right-circularly polarized wave propagating in the $-z$ direction,

$$ \mathbf E_2 = E_0 \operatorname{Re} \left[ (\hat{\mathbf x}-i\hat{\mathbf y}) e^{i(kz+\omega t)} \right]. $$

Therefore,

$$ \boxed{ \mathbf E_2 = E_0 \left[ \hat{\mathbf x}\cos(kz+\omega t) + \hat{\mathbf y}\sin(kz+\omega t) \right] }. $$

Superposition

The total electric field is

$$ \mathbf E=\mathbf E_1+\mathbf E_2. $$

Using the trigonometric identities

$$ \cos(A-B)+\cos(A+B)=2\cos A\cos B, $$

and

$$ \sin(A-B)+\sin(A+B)=2\sin A\cos B, $$

we obtain

$$ \boxed{ \mathbf E = 2E_0\cos\omega t \left( \hat{\mathbf x}\cos kz + \hat{\mathbf y}\sin kz \right) }. $$

Interpretation

At a fixed value of $z$, the vector

$$ \hat{\mathbf x}\cos kz+\hat{\mathbf y}\sin kz $$

has a fixed direction. Therefore, at any particular position, the electric field oscillates back and forth along a fixed line.

Thus the resulting field is linearly polarized at every fixed position, although the direction of that linear polarization changes as we move along the $z$-axis.

For example:

At $z=0$:

$$ \mathbf E=2E_0\hat{\mathbf x}\cos\omega t. $$

At $z=\lambda/4$:

$$ \mathbf E=2E_0\hat{\mathbf y}\cos\omega t. $$

Thus the polarization direction rotates spatially as we move along the propagation axis.

Magnetic field

For a plane wave,

$$ c\mathbf B=\hat{\mathbf k}\times\mathbf E. $$

For the two counter-propagating waves,

$$ c\mathbf B = \hat{\mathbf z}\times\mathbf E_1 - \hat{\mathbf z}\times\mathbf E_2. $$

After simplification,

$$ \boxed{ c\mathbf B = -2E_0\sin\omega t \left( \hat{\mathbf x}\cos kz + \hat{\mathbf y}\sin kz \right) }. $$

Hence

$$ \boxed{ \mathbf B = -\frac{2E_0}{c}\sin\omega t \left( \hat{\mathbf x}\cos kz + \hat{\mathbf y}\sin kz \right) }. $$

Notice that $\mathbf E$ and $\mathbf B$ are parallel rather than perpendicular. This does not contradict the properties of a single plane electromagnetic wave because the total field here is a superposition of two oppositely propagating waves.


(b) Both waves are LCP

Now suppose both counter-propagating waves have left-circular polarization.

For the wave propagating along $+z$,

$$ \mathbf E_1 = E_0 \left[ \hat{\mathbf x}\cos(kz-\omega t) + \hat{\mathbf y}\sin(kz-\omega t) \right]. $$

For the LCP wave propagating along $-z$,

$$ \mathbf E_2 = E_0 \left[ \hat{\mathbf x}\cos(kz+\omega t) - \hat{\mathbf y}\sin(kz+\omega t) \right]. $$

Adding them gives

$$ \mathbf E = E_0\hat{\mathbf x} [ \cos(kz-\omega t)+\cos(kz+\omega t) ] $$ $$ + E_0\hat{\mathbf y} [ \sin(kz-\omega t)-\sin(kz+\omega t) ]. $$

Using

$$ \cos(A-B)+\cos(A+B)=2\cos A\cos B $$

and

$$ \sin(A-B)-\sin(A+B)=-2\cos A\sin B, $$

we obtain

$$ \boxed{ \mathbf E = 2E_0\cos kz \left( \hat{\mathbf x}\cos\omega t - \hat{\mathbf y}\sin\omega t \right) }. $$

Interpretation

Here the spatial dependence appears as the amplitude factor

$$ 2E_0\cos kz, $$

while the direction of the electric field changes with time.

Therefore the electric-field vector rotates in the $xy$-plane.

The magnetic field is

$$ \boxed{ c\mathbf B = 2E_0\sin kz \left( \hat{\mathbf x}\cos\omega t - \hat{\mathbf y}\sin\omega t \right) }. $$

or

$$ \boxed{ \mathbf B = \frac{2E_0}{c}\sin kz \left( \hat{\mathbf x}\cos\omega t - \hat{\mathbf y}\sin\omega t \right) }. $$

Comparison

(a) LCP + RCP (b) LCP + LCP
Electric field $2E_0\cos\omega t(\hat{x}\cos kz+\hat{y}\sin kz)$ $2E_0\cos kz(\hat{x}\cos\omega t-\hat{y}\sin\omega t)$
Spatial dependence Direction Amplitude
Time dependence Amplitude Direction
Field at fixed position Linear oscillation Rotating vector
Character Standing-wave field Standing-wave field

Interpretation of $R(z)$ as the Radius of Curvature

We now consider a Gaussian beam. The phase of the beam, neglecting the Gouy phase $\alpha(z)$, can be written as

$$ \Phi(\rho,z,t) = kz+ \frac{k\rho^2}{2R(z)} -\omega t. $$

The quantity $R(z)$ is given by

$$ \boxed{ R(z) = z\left[ 1+\left(\frac{z_R}{z}\right)^2 \right] } $$

or equivalently,

$$ \boxed{ R(z)=z+\frac{z_R^2}{z}. } $$

We want to understand why $R(z)$ can be interpreted as the radius of curvature of a constant-phase surface.

Constant-phase surface

At a fixed time, a surface of constant phase satisfies

$$ kz+\frac{k\rho^2}{2R(z)} = \text{constant}. $$

Dividing by $k$,

$$ z+\frac{\rho^2}{2R(z)} = \text{constant}. $$

The important feature here is the quadratic dependence on $\rho$.

Geometry of a sphere

Consider a sphere of radius $R$ and a point near its axis. Let $\rho$ be the transverse distance from the axis and let $\Delta z$ be the longitudinal displacement of the surface from the reference point.

From the geometry of the sphere,

$$ R^2=(R-\Delta z)^2+\rho^2. $$

Expanding the right-hand side gives

$$ R^2 = R^2-2R\Delta z+(\Delta z)^2+\rho^2. $$

Canceling $R^2$,

$$ 0=-2R\Delta z+(\Delta z)^2+\rho^2. $$

Paraxial approximation

We are interested in points close to the propagation axis, so $\rho\ll R$. Consequently $\Delta z\ll R$, and the term $(\Delta z)^2$ can be neglected.

Therefore,

$$ 0\approx-2R\Delta z+\rho^2. $$

Hence,

$$ \boxed{ \Delta z\approx\frac{\rho^2}{2R}. } $$

This is the key geometric result.

Comparison with the Gaussian beam phase

The phase accumulated because of the additional distance $\Delta z$ is approximately

$$ k\Delta z = \frac{k\rho^2}{2R}. $$

Therefore the phase of a spherical wave near its axis has the form

$$ kz+\frac{k\rho^2}{2R}. $$

But this is exactly the transverse phase dependence of the Gaussian beam:

$$ \Phi = kz+ \frac{k\rho^2}{2R(z)} -\omega t. $$

Thus the Gaussian beam has, near its propagation axis, the same phase structure as a spherical wave whose radius of curvature is $R(z)$.

Therefore,

$$ \boxed{ R(z)\text{ is the radius of curvature of the constant-phase surface.} } $$

Behavior at the beam waist

At the waist, $z=0$. Since

$$ R(z)=z+\frac{z_R^2}{z}, $$

we have

$$ \boxed{ R(0)\rightarrow\infty. } $$

A surface with infinite radius of curvature is locally a plane. Hence the wavefront at the beam waist is approximately planar.

Far from the waist

For $|z|\gg z_R$,

$$ \frac{z_R^2}{z}\ll z, $$

so

$$ R(z)\approx z. $$

Thus far from the waist, the Gaussian beam behaves increasingly like a spherical wave whose radius of curvature is approximately the distance from the waist.


Summary

Example 16.2

For oppositely propagating circularly polarized waves, the superposition produces a standing-wave electromagnetic field.

For LCP in $+z$ and RCP in $-z$,

$$ \boxed{ \mathbf E = 2E_0\cos\omega t (\hat{x}\cos kz+\hat{y}\sin kz) } $$

The field is linearly polarized at each fixed position, but the polarization direction changes with $z$.

When both waves are LCP,

$$ \boxed{ \mathbf E = 2E_0\cos kz (\hat{x}\cos\omega t-\hat{y}\sin\omega t) } $$

The amplitude varies with position while the electric-field direction rotates with time.

Example 16.4

The phase of a Gaussian beam contains the term

$$ \frac{k\rho^2}{2R(z)}. $$

A spherical surface near its axis satisfies

$$ \Delta z\approx\frac{\rho^2}{2R}. $$

Therefore the quadratic transverse phase of the Gaussian beam is precisely the phase variation expected from a spherical wavefront. This provides the physical interpretation

$$ \boxed{ R(z)=\text{radius of curvature of the constant-phase surface}. } $$