Stationary States & Superposition
Stationary States & Superposition
The time-dependent Schrödinger equation looks fearsome — a complex PDE — but for time-independent potentials it surrenders to the oldest trick in mathematical physics: separation of variables. The reward is the time-independent equation, whose solutions — stationary states — are the atoms of quantum dynamics. Individually they do nothing at all, like a cat at 2 p.m.; superpose two of them, and the relative phase makes everything move.
Learning Objectives
After this lesson you will be able to:
- Carry out separation of variables on the Schrödinger equation and obtain the time-independent Schrödinger equation .
- Prove that the separation constant must be real and must exceed .
- Derive the three defining properties of stationary states: frozen , constant expectation values, and definite energy.
- Expand an initial state in energy eigenstates via orthonormality and Fourier's trick, interpreting as energy-measurement probabilities.
- Derive the two-state sloshing of the infinite square well and explain why all quantum dynamics is evolving relative phase.
Intuition
Faced with , ask the physicist's first question: are there solutions with trivial time dependence? Yes — products , whose time dependence is a pure phase. The Born rule sees only , so the phase cancels: the probability density is frozen. These are the stationary states, one per allowed energy.
That sounds like a dead end — a theory of motion whose basic solutions never move. The escape is linearity: the general solution is a superposition of stationary states, each spinning its phase at its own rate . In a superposition the phases no longer cancel in ; they beat against each other, and the beats are the dynamics. An electron sloshing in a well, a vibrating bond, a qubit mid-gate — all of it is relative phase between energy eigenstates. The strategy for every problem in Courses P.5–P.6 follows: solve the time-independent equation once for the catalog , then assemble any motion from them.
Theory
Separation of variables
Let and try a product solution . Insert into and divide by :
The left side depends only on , the right only on ; a function of can equal a function of only if both equal the same constant, (the name is not innocent). The PDE splits into two ODEs.
Time part. , so
(the integration constant is absorbed into ): every separable solution wears the same uniform, a phase rotating at — Planck–Einstein again, now as an output.
Space part. The remainder is the time-independent Schrödinger equation (TISE):
— an eigenvalue problem for the Hamiltonian : allowed separation constants are eigenvalues, stationary profiles are eigenfunctions. For bound problems, the admissibility conditions of P.4.1 (normalizability, continuity) select a discrete set : quantization emerges from a boundary-value problem, not from an extra postulate.
must be real, and
Real. If with , then and grows or decays — contradicting conservation of probability (P.4.1). Normalizability for all time forces . (Term 1 language: is Hermitian, so its eigenvalues are real — 0.1.5.)
. Rearrange the TISE:
If everywhere, then everywhere, so has the same sign as at every point: where it curves up, away from the axis; where it curves down, also away. Such a function bends away from zero and cannot decay to it at both ends — it blows up at and is never normalizable. Physically: , so you cannot have less energy than the least potential energy. ( may still be negative if — the bound states of wells, P.5.2.)
Properties of stationary states
Let , normalized. Three properties, one line each:
1. Frozen density. — time-independent; hence stationary.
2. Every expectation value constant. For any with no explicit , the phase passes through and cancels:
Nothing measurable ever changes.
3. Definite energy. Using : , and , so
an energy measurement returns with certainty. Stationary states are states of definite energy.
Caution. A single stationary state predicts nothing moving. Not "slowly" — every probability and every expectation value of every observable is constant. If your system visibly does anything, it is not in a stationary state. Motion — including every interference trick quantum computing plays — lives in superpositions and their evolving relative phases. Stationary states are the alphabet; dynamics is the poetry.
Vocabulary: eigensolutions and degeneracy
Fix the words now, because the rest of the term uses them constantly. A problem whose solutions exist only for a specific set of allowed values of some parameter — here the energy — is an eigenvalue problem; the allowed values are the eigenvalues, and the particular function attached to each is its eigenfunction. Together they form an eigensolution. Since our parameter is an energy, the are eigenenergies and the are energy eigenfunctions. "Stationary state", "energy eigenstate", and "eigensolution of " all name the same object.
One eigenvalue need not have only one eigenfunction. When two or more linearly independent eigenfunctions share a single eigenvalue, the eigenvalue is called degenerate, and the number of independent eigenfunctions belonging to it is its degeneracy. Nothing forbids it, and symmetry tends to cause it: the 1D problems of Course P.5 are all non-degenerate (a second-order ODE with two decaying-tail boundary conditions has one solution per energy), but the moment a problem gains a symmetry direction, degeneracy appears — a particle in a cube has , so , and share one energy, a three-fold degeneracy. The hydrogen atom's -fold degeneracy in and (P.6.2) is the headline example, and lifting degeneracies with fields is how spectroscopy reads atoms apart (P.6.3).
Degeneracy matters practically for the expansion below: within a degenerate set, any linear combination is still an eigenfunction of the same energy, so the basis is not unique — you may (and should) choose combinations adapted to another symmetry, exactly the freedom exploited when a degenerate subspace is diagonalized in 0.1.5.
The general solution: superposition of stationary states
Linearity lets us add separable solutions, and the spectral theorem guarantees every solution arises this way:
This is the master formula of wave mechanics: solve the TISE once, then evolution is "attach the phase wiggles."
Orthonormality and completeness. The eigenfunctions can be chosen with
and they are complete: any admissible expands as . This is the spectral theorem of 0.1.5 Eigenvalues & the Spectral Theorem promoted to infinite dimensions: .
Fourier's trick. Multiply by and integrate; orthonormality collapses the sum:
Exactly the Fourier-coefficient recipe of 0.3.2 — a Fourier series is an eigenfunction expansion (for the infinite well, literally a sine series).
What the mean. Insert the expansion into and ; the cross terms die by orthonormality:
both time-independent (energy is conserved). The reading, confirmed by 1.1.2: is the probability that an energy measurement returns — the Born rule in the energy basis, with its consistency condition.
Dynamics from interference: the sloshing well
To watch phases do something, take the cleanest arena: the infinite square well on , whose stationary states (derived in full in P.5.2) are
Prepare and compute the density (the are real):
and since the bracket is ,
The cross term — pure interference — oscillates at the Bohr frequency . Since on the left half of the well and on the right, the probability lump sloshes left–right with period . Note what mattered: not the absolute phases (a global changes nothing) but the relative phase . All quantum dynamics is relative phase in a superposition. This is also the frequency an atom radiates: , the Bohr condition of P.2.2.
Connections. The phases assemble into the evolution operator — exactly the unitary of 1.1.3 The Evolution Postulate; what we found by separating variables, Term 1 postulates directly. And a stationary state's alone is a global phase — unobservable; between two components it is a relative phase — the whole show: precisely the distinction of 1.1.1, now with a clock attached.
Worked Examples
Example 1 — Energy statistics of a three-term superposition
A particle in the infinite well is prepared in . Check normalization; find the energy-measurement outcomes, probabilities, and .
. ✓ Outcomes are the eigenvalues present: , , (the in never enters — only does). With :
Note is not an eigenvalue: the average need not be a possible outcome. And all these numbers are constants of the motion — measure at any , same statistics.
Example 2 — The sloshing amplitude
For the two-state superposition above, compute .
Each is symmetric about , so the first term is . For the cross integral, use and :
Therefore
the mean position swings across the well at the Bohr frequency . Each ingredient state alone predicts a frozen ; the superposition moves.
Hands-on (Python)
import numpy as np
import matplotlib.pyplot as plt
# --- Two-state sloshing in the infinite square well --------------------------
# Numerical values hbar = m = L = 1 (physics keeps ħ explicit; arrays don't care).
hbar, m, L = 1.0, 1.0, 1.0
x = np.linspace(0, L, 800)
psi_n = lambda n, x: np.sqrt(2/L) * np.sin(n*np.pi*x/L) # √(2/L) sin(nπx/L)
E_n = lambda n: n**2 * np.pi**2 * hbar**2 / (2*m*L**2) # n²π²ħ²/2mL²
w21 = (E_n(2) - E_n(1)) / hbar # Bohr frequency
T = 2*np.pi / w21 # sloshing period
Psi = lambda x, t: (psi_n(1,x)*np.exp(-1j*E_n(1)*t/hbar)
+ psi_n(2,x)*np.exp(-1j*E_n(2)*t/hbar)) / np.sqrt(2)
for frac in [0, 0.25, 0.5, 0.75]: # snapshots across one period
plt.plot(x, np.abs(Psi(x, frac*T))**2, label=f"t = {frac:.2f} T")
plt.xlabel("x/L"); plt.ylabel(r"$|\Psi|^2$"); plt.legend(); plt.show()
# Expected: lump on the left at t=0, symmetric at T/4 and 3T/4, on the right at T/2.
t = np.linspace(0, 2*T, 400)
x_mean = [np.trapz(x*np.abs(Psi(x, tt))**2, x) for tt in t]
plt.plot(t/T, x_mean); plt.axhline(0.5, ls="--", c="gray")
plt.xlabel("t/T"); plt.ylabel(r"$\langle x\rangle$"); plt.show()
# Expected: <x>(t) = 0.5 - (16/9π²)cos(ω21 t) ≈ 0.5 - 0.180 cos(ω21 t):
# a clean cosine at exactly ω21 = (E2 - E1)/ħ.# --- Expand a triangular initial state in well eigenstates -------------------
tri = np.where(x < L/2, x, L - x) # triangle peaked at L/2
tri = tri / np.sqrt(np.trapz(tri**2, x)) # normalize
N = 40 # c_n by numerical quadrature
c = np.array([np.trapz(psi_n(n, x)*tri, x) for n in range(1, N+1)])
print(np.cumsum(np.abs(c)**2)[[0, 2, 9, 39]])
# Expected: ≈ [0.9855 0.9977 0.9998 1.0000] — Σ|c_n|² → 1 (completeness);
# even n vanish by symmetry and |c_n|² ~ 1/n⁴, so convergence is fast.
def Psi_rec(x, t): # reconstruct Σ c_n ψ_n e^{-iE_n t/ħ}
return sum(c[n-1]*psi_n(n, x)*np.exp(-1j*E_n(n)*t/hbar) for n in range(1, N+1))
T1 = 2*np.pi*hbar/E_n(1) # fundamental period
plt.plot(x, tri**2, "k--", label=r"exact $|\Psi(x,0)|^2$")
for tt, lab in [(0, "t=0"), (0.1*T1, "t=0.1$T_1$"), (0.25*T1, "t=0.25$T_1$")]:
plt.plot(x, np.abs(Psi_rec(x, tt))**2, label=lab)
plt.xlabel("x/L"); plt.legend(); plt.show()
# Expected: at t=0 the reconstruction overlays the triangle (dashed); later
# snapshots show the peak melting into interference wiggles — dynamics generated
# purely by the relative phases e^{-iE_n t/ħ}.Exercises
E1 (easy). Verify by substitution that solves the time-dependent Schrödinger equation whenever .
Solution
Left side: $i\hbar,\partial_t\Psi_n = i\hbar(-iE_n/\hbar)\psi_ne^{-iE_nt/\hbar} = E_n\psi_ne^{-iE_nt/\hbar}\hat H\Psi_n = (\hat H\psi_n)e^{-iE_nt/\hbar} = E_n\psi_ne^{-iE_nt/\hbar}x\hat H$). Equal. ✓
E2 (easy). For in the infinite well: which energies can be measured, with what probabilities? What is in units of ? Do the answers change at later times?
Solution
with ; with . . No change: evolution sends , so every is constant — energy statistics are conserved.
E3 (medium). Prove that eigenfunctions of with distinct energies are orthogonal: . (Hint: evaluate two ways.)
Solution
Call the difference . The terms cancel ( real); the kinetic terms give $-\frac{\hbar^2}{2m}\int(\psi_m^\psi_n'' - \psi_m''^\psi_n)dx = -\frac{\hbar^2}{2m}\big[\psi_m^\psi_n' - \psi_m'^\psi_n\big]_{-\infty}^{\infty} = 0$ after two integrations by parts (boundary terms vanish for normalizable states). So . But evaluating directly with the eigenvalue equations (and real eigenvalues, proved in Theory): . Since , the integral vanishes — Hermiticity at work, as in 0.1.5.
E4 (medium). For $\Psi = \frac{1}{\sqrt2}\big(\psi_1e^{-iE_1t/\hbar} + e^{i\alpha}\psi_2e^{-iE_2t/\hbar}\big)\alpha|\Psi|^2$ has the same sloshing form as in Theory but time-shifted. What does this say about versus a global phase?
Solution
The cross term becomes : the relative phase shifts the starting position of the slosh ( starts the lump on the right) but not the frequency. A global phase cancels in entirely. Relative phase: physical initial condition. Global phase: nothing — the verdict of 1.1.1.
E5 (hard). Show that in the infinite well any state revives exactly: with . Why does no such universal revival occur for a generic potential?
Solution
with . After time , the -th term gains . Choose , i.e. : then for every integer , so every coefficient returns exactly (sub-multiples of give nontrivial global phases and fractional revivals). The magic: all are integer multiples of one quantum , so all Bohr frequencies are commensurate. A generic potential has incommensurate level spacings — the relative phases never realign, and the state never exactly recurs.
Checkpoint
- Walk through separation of variables: what plays the role of the separation constant, and which two ODEs result?
- Why must be real, and why must ?
- Name and derive (one line each) the three defining properties of a stationary state.
- Given , how do you find the , and what do , , and mean?
- Nothing about a stationary state changes in time — so where does quantum dynamics come from?
Answers
- Try ; dividing by separates from , each side equaling a constant . Results: (so ) and the TISE .
- Complex makes , violating conservation of probability. If , and share a sign everywhere, so curves away from the axis and cannot be normalizable.
- (i) — the phases cancel; (ii) constant — the phase passes through and cancels; (iii) , , so — definite energy.
- Fourier's trick: (orthonormality projects each coefficient out). = probability of measuring ; = normalization; — all constant in time.
- From superposition: components accumulate relative phases at the Bohr frequencies , which survive in the cross terms of . All quantum dynamics is evolving relative phase.
Further Reading
- [Gri] Griffiths & Schroeter, §2.1 — stationary states; the source of this lesson's structure.
- [Gri] Griffiths & Schroeter, §2.2 — the infinite square well and its superposition dynamics.
- [Sha] Shankar, §4.3 & Ch. 5 — the energy basis and the propagator , bridging to Term 1.
- [ER] Eisberg & Resnick, §5.5–5.7 — separation of variables and the meaning of eigenvalues.
- [Pre] Preskill, Ph219, Ch. 2 — Hamiltonian evolution stated axiomatically, for contrast.
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