Skip to content

HYDROGEN · MATHEMATICAL DERIVATIONS

Twelve worked hydrogen exercises

Predict, calculate and compare. These exercises connect the proofs to the explorers and make the assumptions visible at each step.

Mohamed Haj YousefUpdated 6 min read

Assumptions, results and research status

A guide to the mathematical research programme.

Conventions and how to work

Unless stated otherwise, use the nonrelativistic point-nucleus Coulomb model and the relative-coordinate length a = aμ. The letter K denotes the positive gross energy scale μc²α²/2. The residual exercise is an explicitly synthetic perturbation example. Work out an answer before opening its solution, then use the relevant explorer to check the numerical consequences. [Hydrogen II]

1. Normalize the 1s wavefunction

Take ψ(r) = Cexp(−r/a), with a > 0. Find C and state its dimensions.

Show the worked solution

Normalization gives 1 = 4π|C|²∫₀∞r²exp(−2r/a)dr. The integral is a³/4, so |C|² = 1/(πa³). Choose a real positive C = 1/√(πa³); an overall constant phase does not change position probabilities. The dimensions of ψ are length−3/2. This is why a three-dimensional density has dimensions length−3.

2. Locate the radial peak

For x = r/a, let p(x) = 4x²exp(−2x). Find its nonzero maximum and compare it with the maximum of exp(−2x).

Show the worked solution

The derivative is p′(x) = 8x(1 − x)exp(−2x). It is positive on 0 < x < 1 and negative for x > 1, so the radial maximum is x = 1. The decreasing volume density has its maximum at x = 0. The shell factor x² explains the difference; neither maximum specifies an electron orbit.

3. Calculate the probability inside a sphere

Evaluate the 1s probability inside r = a and inside r = 2a.

Show the worked solution

Integrating p(x) gives F(x) = 1 − exp(−2x)(1 + 2x + 2x²). Hence F(1) = 1 − 5exp(−2) ≈ 0.323324 and F(2) = 1 − 13exp(−4) ≈ 0.761897. Check these in the probability explorer. The most probable radial separation and the radius containing a specified probability are different measures.

4. Find the mean and variance of the radius

Use the normalized radial density to calculate ⟨r⟩, ⟨r²⟩ and Var(r).

Show the worked solution

Using ∫₀∞xᵏexp(−2x)dx = k!/2k+1, one obtains ⟨r⟩ = 3a/2 and ⟨r²⟩ = 3a². Therefore Var(r) = 3a² − 9a²/4 = 3a²/4 and the standard deviation is √3a/2. The distribution is broad; a single characteristic length does not mean that all detections occur near one radius.

5. Check the equality case in the energy bound

For H = −D∇² − A/r and a = 2D/A, use the square-completion identity to identify the lowest energy.

Show the worked solution

The identity is ⟨ψ,Hψ⟩ + (D/a²)‖ψ‖² = D∫|∇ψ + r̂ψ/a|²d³r. The right-hand side is nonnegative. The normalized exponential obeys ∇ψ = −r̂ψ/a and attains zero. Thus E₁ = −D/a² = −A²/(4D). Existence of this state for every A > 0 also demonstrates why binding by itself does not select a unique coupling.

6. Derive a scale-independent interval ratio

Let Eₙ = −K/n². Find the ratio of the positive 2↔3 energy interval to the positive 1↔2 interval.

Show the worked solution

The first interval is K(1/4 − 1/9) = 5K/36; the second is K(1 − 1/4) = 3K/4. Their ratio is 5/27 ≈ 0.185185. The common K cancels. This checks the shape of the gross spectrum, while an absolute interval additionally checks its scale. It does not address whether a particular one-photon transition is allowed.

7. Increase the coupling by ten percent

With masses, c and ℏ fixed, replace α by 1.1α. Predict the changes in aμ, the binding magnitude and the relative RMS speed.

Show the worked solution

The radius is multiplied by 1/1.1 ≈ 0.909091, the binding magnitude by 1.1² = 1.21, and the relative RMS speed by 1.1. The same changed coupling determines all three. In the scales explorer these are illustrative model settings, not alternative measured values for ordinary hydrogen.

8. Take the finite-mass correction consistently

Let M = mₚ/mₑ. Express μ/mₑ, aμ/a₀ and the gross binding ratio to the infinite-proton-mass limit.

Show the worked solution

One has μ/mₑ = M/(M + 1), aμ/a₀ = (M + 1)/M and |E₁|/|E₁,∞| = M/(M + 1). For M ≈ 1836.15, the radius grows by about 0.05446 percent and the binding magnitude decreases by about 0.05443 percent. These are leading nonrelativistic kinematic effects; extra recoil terms belong to the precision treatment.

9. Count the scalar states at n = 3

List the allowed ℓ values and the number of m states at each ℓ. What changes when an independent electron-spin factor is included?

Show the worked solution

The values are ℓ = 0, 1, 2, giving 1, 3 and 5 values of m respectively. The scalar count is 1 + 3 + 5 = 9 = n². Adding a spin-1/2 factor doubles this count to 18 before spin-dependent interactions lift some degeneracies. State counting is not itself a proof of the physical origin of the representation.

10. Retain both endpoints of an interval

In a synthetic model let δEₙℓ/h = Aδℓ0/n³ with A = 8 kHz. Calculate the changes of the signed 1S→2S, 2S→8S and 2S→8D intervals.

Show the worked solution

The level shifts are 8 kHz for 1S, 1 kHz for 2S, 0.015625 kHz for 8S and zero for 8D. Endpoint subtraction gives −7 kHz, −0.984375 kHz and −1 kHz respectively. The last interval retains the lower 2S contribution. The signed 1S→8S shift is −7.984375 kHz, equal to the sum of the first two intervals. These are synthetic model values.

11. Identify a parameter ambiguity

Suppose two possible mechanisms produce proportional response vectors across every chosen transition. Does reducing measurement uncertainty alone distinguish them?

Show the worked solution

No. Proportional columns in the comparison model have the same direction, so only a combination of their amplitudes is constrained by those observables. One needs an independently fixed coefficient or observables for which the response shapes differ. This is an identifiability question, distinct from the numerical precision of a fit.

12. Locate the independent physical assumption

A proposal defines a temporal tick from a measured hydrogen interval and then reproduces that interval. Which result has been checked, and what would strengthen it?

Show the worked solution

The reproduction checks a calibrated model or its internal algebra. It is not an independent prediction of the interval used to define the tick. A stronger check would fix the tick and other model inputs without that interval, then calculate the interval and additional linked observables with a declared error budget. A useful source result may also explain why the calibration applies to another preparation without retuning.

Continue to a research calculation

The exercises establish consequences of the declared model. The next level of work is to explain why its operator and coefficients follow from a specified temporal source. Visit the correspondence problem and collaboration opportunities. For numerical work, use the reproducibility guide.

Sources for this guide

Source manuscripts, version notes, and standard references are listed in the reference library.

SMONAD

Share and cite

Share this page, or keep a clear reference to the work you are reading.

Share options
Cite this page

Cite the website explanation

Use this reference for the explanation on this page. “n.d.” means its first publication date is not specified; the update date is recorded separately.