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Time evolution

Learning objectives

After this chapter, you should be able to:

Sections 4.1–4.7 form the core path through unitary evolution and spin precession. Sections 4.8–4.9 are mathematical extensions, while Sections 4.10–4.11 form an applications track on laboratory pulses and Ramsey interference. Those tracks may be assigned independently after the core.

4.1 The dynamical postulate

Every chapter so far has treated the spin state as something that only changes at the instant of a measurement. Between measurements, we have simply left the state alone. That gap needs to be filled: real experiments involve waiting time, traveling atoms, and applied fields, and the state must be doing something during all of that. This chapter supplies the missing piece. Between measurements, the state of an isolated system evolves according to the time-dependent Schrödinger equation,

iℏddt∣ψ(t)⟩=H^(t)∣ψ(t)⟩.i\hbar\frac{d}{dt}|\psi(t)\rangle=\hat H(t)|\psi(t)\rangle.

The Hamiltonian H^\hat H is the observable associated with energy, and it plays a second role here as the generator of time evolution: the object that tells the state how to change from one instant to the next. Equation (1) is a first-order differential equation for a vector, which means specifying the initial state ∣ψ(0)⟩|\psi(0)\rangle and the Hamiltonian H^(t)\hat H(t) is enough to determine the state at every later time.

When the Hamiltonian does not depend on time, this differential equation has an explicit solution:

∣ψ(t)⟩=U^(t)∣ψ(0)⟩,U^(t)=e−iH^t/ℏ.|\psi(t)\rangle=\hat U(t)|\psi(0)\rangle, \qquad \hat U(t)=e^{-i\hat Ht/\hbar}.

Check directly that this solves equation (1), rather than accepting it purely on authority. Differentiating the defining power series of U^(t)\hat U(t) term by term with respect to tt,

dU^(t)dt=ddt∑n=0∞1n!(−iH^tℏ)n=−iH^ℏU^(t),\frac{d\hat U(t)}{dt} =\frac{d}{dt}\sum_{n=0}^\infty\frac{1}{n!} \left(\frac{-i\hat Ht}{\hbar}\right)^n =-\frac{i\hat H}{\hbar}\hat U(t),

because H^\hat H commutes with every power of itself, so each term of the series differentiates exactly as an ordinary power of tt would. Multiplying both sides by iℏi\hbar and applying the result to ∣ψ(0)⟩|\psi(0)\rangle reproduces equation (1) exactly. This calculation used only that H^\hat H does not depend on time; nothing about spin specifically entered.

Because H^\hat H is Hermitian, the operator U^\hat U built from it is automatically unitary: U^†U^=I^\hat U^\dagger\hat U=\hat I. This single fact has an important consequence. It guarantees that a state’s normalization never drifts as it evolves:

⟨ψ(t)∣ψ(t)⟩=⟨ψ(0)∣U^†U^∣ψ(0)⟩=1.\langle\psi(t)|\psi(t)\rangle =\langle\psi(0)|\hat U^\dagger\hat U|\psi(0)\rangle=1.

So unitary evolution preserves normalization and, more generally, every inner product between two evolving states. Something here can feel paradoxical at first: within the ideal isolated-system model, this evolution is completely deterministic, even though the outcomes of a later projective measurement are probabilistic. The Schrödinger equation itself introduces no random step; the measurement postulate supplies probabilities when a measurement is made.

What an evolution problem is asking

Most two-state dynamics problems, however different they look on the surface, can be organized into the same five-step sequence:

  1. Write the Hamiltonian and choose a basis in which to represent it.

  2. Construct U^(t)\hat U(t) by using energy eigenstates, diagonalizing the matrix, or exploiting Pauli-matrix identities.

  3. Apply U^(t)\hat U(t) to the initial ket.

  4. Project the evolved ket onto the states of the measurement performed at time tt.

  5. Check normalization, the t=0t=0 limit, and any conserved probabilities.

The distinction between steps 3 and 4 is the single most common source of error in this material, so it is worth stating plainly: the ket evolves continuously under U^(t)\hat U(t), but a probability is only ever defined once a measurement question has been specified. Two different choices of final analyzer can reveal very different time dependence from the very same evolving state, so step 4 cannot be skipped or guessed.

For a time-independent Hamiltonian, the exponential in step 2 can always be understood through its power series, which is most useful once H^\hat H has been diagonalized. If H^=V^D^V^†\hat H=\hat V\hat D\hat V^\dagger, with D^\hat D diagonal, then

e−iH^t/ℏ=V^e−iD^t/ℏV^†.e^{-i\hat Ht/\hbar} =\hat V e^{-i\hat Dt/\hbar}\hat V^\dagger.

In words: diagonalize the Hamiltonian, let each diagonal component evolve by its own simple phase, and transform back to the original basis. This is a completely general method for solving the Schrödinger equation, not a trick that happens to work only for spin.

4.2 Energy eigenstates and phases

Let ∣En⟩|E_n\rangle satisfy the time-independent eigenvalue equation

H^∣En⟩=En∣En⟩.\hat H|E_n\rangle=E_n|E_n\rangle.

Because the evolution operator is built from the exponential of H^\hat H, it acts especially simply on one of H^\hat H’s own eigenstates:

∣En,t⟩=e−iEnt/ℏ∣En⟩.|E_n,t\rangle=e^{-iE_nt/\hbar}|E_n\rangle.

Only an overall phase changes here, and Chapter 2 established that an overall phase never affects any measurement probability. For this reason, an energy eigenstate is called a stationary state: every time-independent measurement probability computed from it stays exactly constant, even though the ket itself is visibly changing.

Concept check 4.1

Can a stationary state have a time-dependent ket?

Answer

Yes. Its ket acquires the phase e−iEt/ℏe^{-iEt/\hbar}. The state is called stationary because this overall phase leaves all time-independent measurement probabilities unchanged.

A general initial state need not be a single energy eigenstate; it can be any superposition of them,

∣ψ(0)⟩=∑ncn∣En⟩,|\psi(0)\rangle=\sum_n c_n|E_n\rangle,

and by linearity of the Schrödinger equation, each term simply evolves on its own:

∣ψ(t)⟩=∑ncne−iEnt/ℏ∣En⟩.|\psi(t)\rangle=\sum_n c_ne^{-iE_nt/\hbar}|E_n\rangle.

Here is the key qualitative difference from a single stationary state: the energy probabilities ∣cn∣2|c_n|^2 stay constant, but the relative phases between different terms evolve, at angular frequencies (En−Em)/ℏ(E_n-E_m)/\hbar set by the energy differences. Any observable that mixes different energy eigenstates can therefore vary in time, even though no individual energy probability ever does.

Two energy levels carry phase-clock arrows that advance at different rates. A graph shows constant probabilities in the energy basis but an oscillating probability in a basis that mixes the energy states.

Figure 1:Energy-basis populations stay fixed while the phase clocks advance at rates set by their energies. Only the relative clock angle is observable, and a measurement in a mixing basis converts it into an oscillating probability.

Example 4.1: a two-level superposition

Suppose E+>E−E_+>E_- and

∣ψ(0)⟩=∣E+⟩+∣E−⟩2.|\psi(0)\rangle=\frac{|E_+\rangle+|E_-\rangle}{\sqrt2}.

Removing the physically irrelevant common phase e−iE−t/ℏe^{-iE_-t/\hbar} gives the equivalent representative

∣ψ(t)⟩∼e−iωt∣E+⟩+∣E−⟩2,ω=E+−E−ℏ.|\psi(t)\rangle\sim \frac{e^{-i\omega t}|E_+\rangle+|E_-\rangle}{\sqrt2}, \qquad \omega=\frac{E_+-E_-}{\hbar}.

The energy probabilities remain one half at all times. But in a basis built from coherent sums of ∣E+⟩|E_+\rangle and ∣E−⟩|E_-\rangle, the corresponding probabilities oscillate with frequency ω\omega. If these two energy states are chosen as the zz basis of a spin-12\tfrac12 system, the xx and yy bases are familiar examples of such mixing bases.

Only energy differences drive observable phase changes

For two energy components, the cross term in any measurement probability contains a phase of the form

e−i(En−Em)t/ℏ.e^{-i(E_n-E_m)t/\hbar}.

This predicts an experimentally visible angular frequency ∣En−Em∣/ℏ|E_n-E_m|/\hbar, a useful fact to remember, since it also gives a quick dimensional check: energy divided by ℏ\hbar has units of inverse time, as an angular frequency should. A common phase built from, say, the average energy of two levels drops out of every isolated-system probability, exactly like the overall phase discussed in Section 4.1.

Example 4.2: evolution from a nondiagonal matrix

In the zz basis, consider

H^=E0I^+ℏΩ2σx=(E0ℏΩ/2ℏΩ/2E0).\hat H=E_0\hat I+\frac{\hbar\Omega}{2}\sigma_x =\begin{pmatrix} E_0&\hbar\Omega/2\\ \hbar\Omega/2&E_0 \end{pmatrix}.

The energy eigenstates are ∣+x⟩|+x\rangle and ∣−x⟩|-x\rangle, with energies E0±ℏΩ/2E_0\pm\hbar\Omega/2. Because the identity commutes with σx\sigma_x,

U^(t)=e−iE0t/ℏ(cos⁡Ωt2 I^−isin⁡Ωt2 σx).\hat U(t)=e^{-iE_0t/\hbar} \left(\cos\frac{\Omega t}{2}\,\hat I -i\sin\frac{\Omega t}{2}\,\sigma_x\right).

Applied to ∣+z⟩|+z\rangle, and suppressing the common phase,

∣ψ(t)⟩∼cos⁡Ωt2∣+z⟩−isin⁡Ωt2∣−z⟩.|\psi(t)\rangle\sim \cos\frac{\Omega t}{2}|+z\rangle -i\sin\frac{\Omega t}{2}|-z\rangle.

Therefore

P(z+,t)=cos⁡2Ωt2,P(z−,t)=sin⁡2Ωt2.P(z+,t)=\cos^2\frac{\Omega t}{2},\qquad P(z-,t)=\sin^2\frac{\Omega t}{2}.

Notice what is happening here: the initial state was definite along zz, but the Hamiltonian was not diagonal in the zz basis. It is exactly this mismatch—the off-diagonal entries connecting ∣+z⟩|+z\rangle and ∣−z⟩|-z\rangle—that drives coherent transfer between the two zz outcomes over time.

4.3 Spin in a uniform magnetic field

We now specialize the general machinery above to the physical situation that will occupy the rest of this chapter: a spin in a magnetic field. A magnetic moment in a uniform field has Hamiltonian

H^=−μ^⋅B,\hat H=-\hat{\boldsymbol\mu}\cdot\mathbf B,

the same energy expression introduced in Chapter 1, now promoted to an operator. For a spin-12\tfrac12 particle whose magnetic moment is proportional to its spin, write μ^=γS^\hat{\boldsymbol\mu}=\gamma\hat{\mathbf S}, where γ\gamma is the gyromagnetic ratio. For B=B0z^\mathbf B=B_0\hat{\mathbf z}, this becomes

H^=−γB0S^z=−ℏω02σz,ω0=γB0.\hat H=-\gamma B_0\hat S_z =-\frac{\hbar\omega_0}{2}\sigma_z, \qquad \omega_0=\gamma B_0.

The sign of ω0\omega_0 depends on the sign convention chosen for γ\gamma. Keeping track of that sign carefully, rather than dropping it, avoids silently reversing the direction of precession later on.

Because σz2=I^\sigma_z^2=\hat I, its exponential can be evaluated directly from the power series, without any diagonalization step. Every even power of σz\sigma_z collapses back to I^\hat I, and every odd power collapses back to σz\sigma_z itself: σz3=σz(σz2)=σz\sigma_z^3=\sigma_z(\sigma_z^2)=\sigma_z, σz4=(σz2)2=I^\sigma_z^4=(\sigma_z^2)^2=\hat I, and so on. Writing θ=ω0t/2\theta=\omega_0t/2 for brevity and separating the exponential’s power series into its even and odd terms,

eiθσz=∑n=0∞(iθσz)nn!=(∑n even(iθ)nn!)⏟=cos⁡θI^+(∑n odd(iθ)nn!)⏟=isin⁡θσz,e^{i\theta\sigma_z} =\sum_{n=0}^\infty\frac{(i\theta\sigma_z)^n}{n!} =\underbrace{\left(\sum_{n\ \mathrm{even}}\frac{(i\theta)^n}{n!}\right)} _{=\cos\theta}\hat I +\underbrace{\left(\sum_{n\ \mathrm{odd}}\frac{(i\theta)^n}{n!}\right)} _{=i\sin\theta}\sigma_z,

using σzn=I^\sigma_z^n=\hat I for even nn and σzn=σz\sigma_z^n=\sigma_z for odd nn to pull σz\sigma_z out of every odd term. The two bracketed sums are exactly the ordinary Taylor series whose sum is cos⁡θ\cos\theta and isin⁡θi\sin\theta respectively: the same series reviewed above for eiϕe^{i\phi}, now split into its even and odd parts instead of read off directly. This gives

eiω0tσz/2=cos⁡ω0t2 I^+isin⁡ω0t2 σz.e^{i\omega_0t\sigma_z/2} =\cos\frac{\omega_0t}{2}\,\hat I +i\sin\frac{\omega_0t}{2}\,\sigma_z.

The identical argument applies to eiα n⋅σ/2e^{i\alpha\,\mathbf n\cdot\boldsymbol\sigma/2} for any unit vector n\mathbf n, since (n⋅σ)2=I^(\mathbf n\cdot\boldsymbol\sigma)^2=\hat I as well; this is exactly the fact reused in Section 4.5 for a field pointing in an arbitrary direction and in Section 4.10 for a general control pulse.

In the zz basis, where H^\hat H is already diagonal, this is simply

U^(t)=(eiω0t/200e−iω0t/2).\hat U(t)= \begin{pmatrix} e^{i\omega_0t/2}&0\\ 0&e^{-i\omega_0t/2} \end{pmatrix}.

Concept check 4.2

A spin begins in ∣+z⟩|+z\rangle in a uniform zz-directed field. Does it precess into ∣−z⟩|-z\rangle?

Answer

No. It is an energy eigenstate and gains only an overall phase. A state with a component transverse to the field has a Bloch vector that visibly precesses.

4.4 Larmor precession

The matrix above shows that a z+z+ or z−z- state, being an eigenstate of H^\hat H, only picks up a phase and never changes. To see the field actually do something visible, we need a state with some component transverse to zz. Prepare ∣+x⟩=(∣+z⟩+∣−z⟩)/2|+x\rangle=(|+z\rangle+|-z\rangle)/\sqrt2 and let it evolve in the zz-directed field. Then

∣ψ(t)⟩=12(eiω0t/2∣+z⟩+e−iω0t/2∣−z⟩).|\psi(t)\rangle=\frac{1}{\sqrt2} \left(e^{i\omega_0t/2}|+z\rangle +e^{-i\omega_0t/2}|-z\rangle\right).

After removing an overall phase, the relative phase between the two terms is e−iω0te^{-i\omega_0t}, and Chapter 2 already showed exactly what a relative phase like this does to measurement probabilities in a different basis. The probabilities for a later SxS_x measurement are

P(x+,t)=cos⁡2ω0t2,P(x−,t)=sin⁡2ω0t2.P(x+,t)=\cos^2\frac{\omega_0t}{2}, \qquad P(x-,t)=\sin^2\frac{\omega_0t}{2}.

Meanwhile P(z+)=P(z−)=1/2P(z+)=P(z-)=1/2 at every time tt: the zz-basis populations never change at all. Geometrically, the Bloch vector simply rotates around the zz axis at the Larmor angular frequency ∣ω0∣|\omega_0|. This is the general pattern to remember: dynamics changes a relative phase, and it is the choice of final analyzer that converts an otherwise hidden phase into a measurable probability.

A Bloch vector traces a circle around a magnetic field directed along z. Beside it, x plus and x minus probabilities oscillate while both z probabilities remain fixed at one half.

Figure 2:Larmor precession leaves the zz-basis populations unchanged but moves the Bloch vector around the equator. An xx analyzer reveals this motion as complementary oscillations in its two output probabilities.

Concept check 4.3

A spin in a zz-directed field always has P(z+)=P(z−)=1/2P(z+)=P(z-)=1/2. Must its state be constant in time?

Answer

No. Its relative phase may evolve even while its zz probabilities remain fixed. An xx or yy analyzer can reveal that phase evolution through changing counts. A single measurement basis does not provide complete state information.

This experiment is a two-state interferometer, in the same spirit as the recombination experiments of Chapters 1 and 2. Preparing ∣+x⟩|+x\rangle creates two equal zz-basis amplitudes, the field gives them different phases as time passes, and the final xx analyzer recombines those amplitudes into an interference pattern. The observed oscillation is the spin-space analog of moving a phase plate through one arm of an ordinary path interferometer.

Screenshot of the Quantum Measurement: Bloch Sphere simulation

Figure 3:Prepare ∣+x⟩|+x\rangle, switch on a zz-directed field, and watch the Bloch vector sweep around the equator at the Larmor frequency exactly as equation (25) predicts, while a live readout of P(x±,t)P(x\pm,t) confirms equation (26).

Interactive simulation: Quantum Measurement: Bloch Sphere

The classical system with the same equation of motion is a gyroscope: a torque perpendicular to an angular momentum does not tip it over but walks it around a cone at fixed polar angle, exactly as a transverse field walks the Bloch vector around the equator without changing P(z±)P(z\pm).

Screenshot of the Precession simulation

Figure 4:A spinning top under gravity, precessing steadily about the vertical. ∣L⃗∣|\vec L| and LzL_z stay fixed while LxL_x and LyL_y trace out a circle—the classical motion behind the Bloch vector’s rotation above, and behind the orbital-angular-momentum vector model of Chapter 9.

Interactive simulation: Precession

Example 4.3: a spin-flip time

Starting from ∣+x⟩|+x\rangle, the first time at which an SxS_x measurement gives x−x- with certainty satisfies ∣ω0∣t=π|\omega_0|t=\pi. Thus

tflip=π∣ω0∣.t_{\text{flip}}=\frac{\pi}{|\omega_0|}.

Be precise about what this is not: it is not a transition between the SzS_z energy levels, since their populations remain fixed throughout. It is a rotation of the state relative to the xx measurement basis—the energy eigenstates are untouched; only the relative phase between them has advanced by π\pi.

Example 4.4: infer a field from counts

A +x+x state evolves for 2.0 μs2.0\,\mu\text{s} in a zz-directed field. A later SxS_x measurement gives P(x+)=3/4P(x+)=3/4. Equation (26) implies

cos⁡2ω0t2=34.\cos^2\frac{\omega_0t}{2}=\frac34.

The smallest positive phase is ∣ω0∣t=π/3|\omega_0|t=\pi/3, giving

∣ω0∣=π3t≈5.24×105 rad s−1.|\omega_0|=\frac{\pi}{3t} \approx5.24\times10^5\ \text{rad s}^{-1}.

Two ambiguities remain, and neither should be overlooked. The probability alone does not determine the sign of ω0\omega_0, since cos⁡2\cos^2 cannot distinguish clockwise from counterclockwise rotation. And because the cosine is periodic, this same data is also consistent with larger frequencies differing by whole cycles. Additional measurements at other times, or a yy analyzer sensitive to the direction of rotation, remove these ambiguities.

4.5 A field in an arbitrary direction

Everything so far assumed the field points along zz. For a constant field along an arbitrary unit vector n\mathbf n,

H^=−ℏω2n⋅σ.\hat H=-\frac{\hbar\omega}{2}\mathbf n\cdot\boldsymbol\sigma.

Since (n⋅σ)2=I^(\mathbf n\cdot\boldsymbol\sigma)^2=\hat I—the same identity used in Chapter 3—the same power-series trick used for σz\sigma_z generalizes immediately:

U^(t)=cos⁡ωt2 I^+isin⁡ωt2 n⋅σ.\hat U(t)= \cos\frac{\omega t}{2}\,\hat I +i\sin\frac{\omega t}{2}\,\mathbf n\cdot\boldsymbol\sigma.

This operator rotates the Bloch vector around n\mathbf n, and it also reveals why the exponent naturally involves a half-angle, echoing the half-angle rule from Chapter 1. A 2π2\pi spatial rotation gives U^=−I^\hat U=-\hat I, and only a 4π4\pi rotation returns the ket to exactly itself. That minus sign after 2π2\pi is an overall phase for one isolated evolving path, so it has no effect by itself, but it becomes observable through interference with a second, unrotated path.

Three geometric cases deserve separate attention. If the initial Bloch vector is parallel to n\mathbf n, the state is an energy eigenstate and gains only an overall phase, never changing direction. If it starts perpendicular to n\mathbf n, it sweeps out a full circle around n\mathbf n. At any intermediate angle, it traces a cone around n\mathbf n, with its component along n\mathbf n staying fixed throughout.

Example 4.5: rotation about xx

Take the Hamiltonian H^=−(ℏω/2)σx\hat H=-(\hbar\omega/2)\sigma_x and initial state ∣+z⟩|+z\rangle. Equation (31) gives

∣ψ(t)⟩=cos⁡ωt2∣+z⟩+isin⁡ωt2∣−z⟩.|\psi(t)\rangle =\cos\frac{\omega t}{2}|+z\rangle +i\sin\frac{\omega t}{2}|-z\rangle.

The probability of a z−z- result is sin⁡2(ωt/2)\sin^2(\omega t/2). At ∣ω∣t=π/2|\omega|t=\pi/2, the state has equal zz probabilities but a definite transverse direction; at ∣ω∣t=π|\omega|t=\pi, it is ∣−z⟩|-z\rangle up to phase. Equal zz populations halfway through the rotation do not mean coherence has been lost, however: the state is still a perfectly definite pure state, just one pointing along a different axis.

4.6 Measurement interrupts unitary evolution

So far we have evolved a state continuously and only asked about measurement at the very end. Real experimental protocols often measure, select an outcome, and then let the resulting state evolve further, and it is important to know exactly how to handle that. Suppose the spin evolves until time t1t_1, when SxS_x is measured. Just before the measurement,

∣ψ(t1)⟩=U^(t1)∣ψ(0)⟩.|\psi(t_1)\rangle=\hat U(t_1)|\psi(0)\rangle.

The outcome probabilities follow from projecting this state onto ∣±x⟩|\pm x\rangle, exactly as in Chapter 3. If the result is x+x+, the state used for all subsequent evolution is ∣+x⟩|+x\rangle itself, not the pre-measurement superposition:

∣ψ(t>t1)⟩=U^(t,t1)∣+x⟩.|\psi(t>t_1)\rangle=\hat U(t,t_1)|+x\rangle.

Unitary evolution and ideal projective measurement are two genuinely distinct parts of the model, governed by different rules, and confusing them leads to a common mistake: continuing to evolve the pre-measurement superposition after a definite outcome has already been selected, as if the measurement had never happened.

Example 4.6: a complete prepare–evolve–measure protocol

A spin is prepared in ∣+x⟩|+x\rangle, evolves in a zz-directed field for a time t1=π/(2∣ω0∣)t_1=\pi/(2|\omega_0|), and is measured along xx. Suppose the x−x- outcome is selected. The same field then acts for another time t2=π/(2∣ω0∣)t_2=\pi/(2|\omega_0|) before a final SxS_x measurement.

Just before the intermediate measurement, P(x+)=P(x−)=1/2P(x+)=P(x-)=1/2. Selecting x−x- prepares ∣−x⟩|-x\rangle; it does not leave the earlier phase-evolved ket in place, per the rule just stated. Starting fresh from ∣−x⟩|-x\rangle, another quarter-period of evolution produces equal final xx probabilities. So the probability for either final result, conditional on having selected the x−x- branch, is 1/21/2. The probability for the complete route starting from the original preparation must also include the probability of the intermediate selection itself, giving 1/41/4 overall.

4.7 Constants in the Hamiltonian

Adding a constant energy E0E_0 to every state changes the Hamiltonian to H^′=H^+E0I^\hat H'=\hat H+E_0\hat I. Because E0I^E_0\hat I commutes with anything, the corresponding evolution operator factors cleanly:

U^′(t)=e−iE0t/ℏU^(t).\hat U'(t)=e^{-iE_0t/\hbar}\hat U(t).

Every state acquires exactly the same overall phase from this shift, so isolated-system probabilities are completely unchanged. This confirms a pattern seen throughout the chapter: it is energy differences, not an arbitrary choice for the zero of energy, that control observable relative phases.

4.8 Optional mathematical extension: time-dependent Hamiltonians

Every result so far assumed a time-independent Hamiltonian, which is what let us write U^(t)=e−iH^t/ℏ\hat U(t)=e^{-i\hat Ht/\hbar} so simply. If H^\hat H instead changes with time, that simple exponential formula no longer applies, and the evolution operator must instead be defined through its own differential equation:

iℏdU^(t,t0)dt=H^(t)U^(t,t0),U^(t0,t0)=I^.i\hbar\frac{d\hat U(t,t_0)}{dt} =\hat H(t)\hat U(t,t_0), \qquad \hat U(t_0,t_0)=\hat I.

If the Hamiltonians at different times all commute with each other, the solution still takes a simple exponential form, just with an integral in place of a product:

U^(t,t0)=exp⁡[−iℏ∫t0tH^(t′) dt′].\hat U(t,t_0)= \exp\left[-\frac{i}{\hbar} \int_{t_0}^{t}\hat H(t')\,dt'\right].

But if [H^(t1),H^(t2)]≠0[\hat H(t_1),\hat H(t_2)]\ne0 for some pair of times, this shortcut fails, and the ordering of successive infinitesimal rotations genuinely matters; a time-ordered exponential or a piecewise product must be used instead. For example, a pulse about xx followed by a pulse about yy generally does not produce the same final state as the reversed sequence. This is the dynamical counterpart of the noncommuting analyzer questions from Chapter 3.

Example 4.7: a piecewise-constant Hamiltonian

Suppose a control system applies

H^(t)={(ℏΩ/2)σx,0≤t<τ,(ℏΩ/2)σz,τ≤t<2τ,Ωτ=π2.\hat H(t)= \begin{cases} (\hbar\Omega/2)\sigma_x,&0\leq t<\tau,\\ (\hbar\Omega/2)\sigma_z,&\tau\leq t<2\tau, \end{cases} \qquad \Omega\tau=\frac{\pi}{2}.

Within each interval the Hamiltonian is constant. The complete evolution is therefore the ordered product

U^(2τ,0)=R^z(π/2)⏟second intervalR^x(π/2)⏟first interval.\hat U(2\tau,0) =\underbrace{\hat R_z(\pi/2)}_{\text{second interval}} \underbrace{\hat R_x(\pi/2)}_{\text{first interval}}.

The earliest operation stands nearest the initial ket. Starting from ∣+z⟩|+z\rangle, the first interval gives R^x(π/2)∣+z⟩=∣−y⟩\hat R_x(\pi/2)|+z\rangle=|-y\rangle. Applying the zz rotation then gives

R^z(π/2)∣−y⟩=e−iπ/4∣+x⟩.\hat R_z(\pi/2)|-y\rangle =e^{-i\pi/4}|+x\rangle.

The displayed phase is overall, so the final Bloch direction is +x+x. If the two intervals are reversed, the zz pulse first changes ∣+z⟩|+z\rangle only by an overall phase, after which the xx pulse leaves the Bloch vector at −y-y. The two schedules use the same Hamiltonians for the same durations but end in different physical states because the interval propagators do not commute. This piecewise construction is the practical finite-step version of time ordering.

4.9 Optional mathematical extension: motion of expectation values

The Schrödinger equation for the ket also implies a direct equation of motion for the expectation value of any observable, which is often a faster route to physical insight than tracking the full ket. For an operator with no explicit time dependence of its own,

ddt⟨A⟩=iℏ⟨[H^,A^]⟩.\frac{d}{dt}\langle A\rangle =\frac{i}{\hbar}\langle[\hat H,\hat A]\rangle.

Specializing to H^=−γB⋅S^\hat H=-\gamma\mathbf B\cdot\hat{\mathbf S} and using the spin commutators from Chapter 3, this becomes

ddt⟨S⟩=γ⟨S⟩×B.\frac{d}{dt}\langle\mathbf S\rangle =\gamma\langle\mathbf S\rangle\times\mathbf B.

Equation (42) has exactly the form of classical magnetic precession, even though each individual component measurement remains fully quantized, with only two discrete outcomes. It offers a useful bridge between two pictures developed so far: the geometric Bloch-sphere picture of Chapter 2, and the explicit matrix evolution of a ket developed in this chapter. The expectation vector traces out a smooth, classical-looking trajectory, even though the individual Stern–Gerlach outcomes behind it remain discrete.

4.10 Applications track: controlled rotations and pulse language

Laboratory control of a spin is usually described not in terms of a continuously running field, but in terms of discrete pulses—a field switched on for a controlled duration to produce a specific rotation. A constant control Hamiltonian applied for a chosen duration implements exactly such a rotation. Define

R^n(α)=exp⁡(−iα2n⋅σ)=cos⁡α2I^−isin⁡α2n⋅σ.\hat R_{\mathbf n}(\alpha) =\exp\left(-i\frac{\alpha}{2}\mathbf n\cdot\boldsymbol\sigma\right) =\cos\frac{\alpha}{2}\hat I -i\sin\frac{\alpha}{2}\mathbf n\cdot\boldsymbol\sigma.

For H^=(ℏΩ/2)n⋅σ\hat H=(\hbar\Omega/2)\mathbf n\cdot\boldsymbol\sigma applied for time τ\tau, the rotation angle is α=Ωτ\alpha=\Omega\tau. This control Hamiltonian is defined with the opposite sign from the field Hamiltonian H^=−(ℏω/2)n⋅σ\hat H=-(\hbar\omega/2)\mathbf n\cdot\boldsymbol\sigma of Sections 4.3–4.5; matching the two conventions, Ω=−ω\Omega=-\omega, recovers R^n(Ωτ)=U^(τ)\hat R_{\mathbf n}(\Omega\tau)=\hat U(\tau) from equation (31). Two particular pulses come up often enough to deserve names: a π\pi pulse carries a Bloch vector to the opposite side of its rotation circle, while a π/2\pi/2 pulse can turn a definite zz state into an equal-amplitude superposition. For example,

R^y(π2)∣+z⟩=∣+x⟩,R^x(π)∣+z⟩=−i∣−z⟩.\hat R_y\left(\frac{\pi}{2}\right)|+z\rangle=|+x\rangle, \qquad \hat R_x(\pi)|+z\rangle=-i|-z\rangle.

The factor −i-i may be dropped here because it multiplies the entire state; subsequent unitary operations cannot turn a truly global phase into a relative one. In multibranch calculations, however, a phase belonging to only one branch is not global and must be retained until the branches are recombined.

If an xx pulse acts first and a yy pulse second, the combined operator is

∣ψf⟩=R^y(β)R^x(α)∣ψi⟩.|\psi_{\mathrm f}\rangle =\hat R_y(\beta)\hat R_x(\alpha)|\psi_{\mathrm i}\rangle.

Read this expression from right to left: the earliest operation in time stands closest to the initial ket. Rotations about different axes generally do not commute, so reversing the order of these two matrices describes a genuinely different laboratory sequence, not merely a different way of writing the same one.

Example 4.8: pulse order on a prepared spin

Begin in ∣+z⟩|+z\rangle. An xx-axis π/2\pi/2 pulse produces

R^x(π2)∣+z⟩=∣+z⟩−i∣−z⟩2=∣−y⟩.\hat R_x\left(\frac{\pi}{2}\right)|+z\rangle =\frac{|+z\rangle-i|-z\rangle}{\sqrt2}=|-y\rangle.

A subsequent yy-axis pulse changes this SyS_y eigenstate only by an overall phase, since ∣−y⟩|-y\rangle is already an eigenstate of the rotation axis. In the reverse order, the first yy pulse produces ∣+x⟩|+x\rangle, which the xx pulse then changes only by an overall phase, for the same reason. The two final Bloch vectors, −y-y and +x+x, are clearly different states. This geometric shortcut reaches the same conclusion as direct matrix multiplication, with considerably less arithmetic.

Two pulse sequences start from z plus and apply the same x-axis and y-axis pi over two pulses in opposite orders. One sequence ends at minus y and the reversed sequence ends at plus x.

Figure 5:The same two control pulses lead to different final states when their order is reversed. The laboratory sequence runs left to right, while the corresponding operator product acts on the ket from right to left.

4.11 Applications track: Ramsey interference

We can now assemble everything in this chapter into one of the most important protocols in atomic physics: a Ramsey sequence, which is really an interferometer built entirely in a two-state space, using pulses instead of beam splitters. The protocol has five steps:

  1. prepare ∣+z⟩|+z\rangle;

  2. apply R^y(π/2)\hat R_y(\pi/2) to create ∣+x⟩|+x\rangle;

  3. allow free phase evolution for time TT;

  4. apply R^y(−π/2)\hat R_y(-\pi/2); and

  5. measure SzS_z.

Represent the free evolution in step 3 by

U^free(T)=R^z(δT)=(e−iδT/200eiδT/2),\hat U_{\mathrm{free}}(T) =\hat R_z(\delta T) =\begin{pmatrix} e^{-i\delta T/2}&0\\ 0&e^{i\delta T/2} \end{pmatrix},

where δ\delta is the relative angular frequency in the chosen reference frame. Combining all five steps, the final state is

∣ψf⟩=R^y(−π2)R^z(δT)R^y(π2)∣+z⟩.|\psi_{\mathrm f}\rangle =\hat R_y\left(-\frac{\pi}{2}\right) \hat R_z(\delta T) \hat R_y\left(\frac{\pi}{2}\right)|+z\rangle.

Projecting onto ∣±z⟩|\pm z\rangle gives the observed fringes

P(z+)=cos⁡2δT2=1+cos⁡(δT)2,P(z−)=sin⁡2δT2.P(z+)=\cos^2\frac{\delta T}{2} =\frac{1+\cos(\delta T)}2,\qquad P(z-)=\sin^2\frac{\delta T}{2}.

It is worth naming what each step contributes: the first pulse creates two coherent amplitudes out of a single definite state, free evolution changes their relative phase by an amount set by δ\delta and TT, and the second pulse recombines those two amplitudes so that the final measurement can read out the accumulated phase as a probability. This is precisely the coherent path logic first introduced in Chapter 2, now implemented with controlled rotations rather than physically separated paths.

A Ramsey sequence prepares z plus, applies a pi over two pulse, allows free phase evolution, applies a reverse pi over two pulse, and measures z. A graph below shows complementary z plus and z minus interference fringes versus accumulated phase.

Figure 6:A Ramsey experiment is a two-state interferometer: the first pulse splits an amplitude, free evolution shifts the relative phase, and the second pulse recombines the alternatives. The final SzS_z counts trace the accumulated phase as complementary fringes.

Example 4.9: the first fringe minimum

If ∣δ∣=2π(25 kHz)|\delta|=2\pi(25\,\mathrm{kHz}), the first z+z+ minimum occurs at ∣δ∣T=π|\delta|T=\pi:

Tmin⁡=π∣δ∣=20 μs.T_{\min}=\frac{\pi}{|\delta|}=20\,\mu\mathrm{s}.

Scanning TT at fixed detuning reveals these oscillations directly. Scanning the control frequency instead, at fixed TT, also produces fringes, now as a function of detuning rather than time. This sensitivity of a simple probability to a small phase is the operating principle behind atomic clocks and many modern quantum sensors.

If the accumulated phase varies unpredictably between different trials of the experiment, averaging over those trials reduces the fringe contrast. Each individual run may still be perfectly unitary; it is the pooled ensemble that becomes mixed, because its relative phase is no longer controlled from run to run. Density operators, introduced in Chapter 3, are exactly the tool needed to distinguish this loss of ensemble coherence from ordinary, coherent precession.

Concept check 4.4

Why not measure SzS_z after the first Ramsey pulse to verify both alternatives?

Answer

That measurement would make the alternatives distinguishable and remove their coherence. If its outcomes were pooled, the second pulse would yield equal final zz probabilities rather than a full-contrast fringe.

Summary

Exercises

Exercises 1–9 establish the core evolution and measurement workflow. Exercises 10–13 consolidate spin precession and interrupted evolution. Exercises 14–20 support the optional mathematical and applications tracks; a focused first assignment need not include all three groups.

  1. Starting from equation (1), show directly that the norm of a state is constant when H^\hat H is Hermitian.

  2. A two-level system has energies 0 and ϵ\epsilon. Evolve the initial state (∣E0⟩+i∣E1⟩)/2(|E_0\rangle+i|E_1\rangle)/\sqrt2 and find the probability of returning to the initial state at time tt.

  3. Derive equation (23) by separating the exponential power series into even and odd powers.

  4. Derive equation (26) from equation (25) using inner products.

  5. For the same evolving state, calculate P(y+,t)P(y+,t) and identify the direction of precession for positive ω0\omega_0 under the conventions used here.

  6. Find the earliest time at which a spin initially in ∣+z⟩|+z\rangle becomes ∣−z⟩|-z\rangle under a uniform field in the +x+x direction.

  7. Prove that equation (31) is unitary.

  8. An SxS_x measurement is made halfway through a full Larmor period and its x+x+ result is selected. Describe the state immediately before and after the measurement, then find P(x+)P(x+) one quarter-period later.

  9. Show that adding E0I^E_0\hat I to a Hamiltonian cannot affect the expectation value of any time-independent observable in an isolated system.

  10. For the Hamiltonian in Example 4.2, calculate P(y+,t)P(y+,t) for an initial ∣+z⟩|+z\rangle state. At what earliest time is the state ∣+y⟩|+y\rangle up to overall phase?

  11. A +x+x state precesses in a zz-directed field. Find both P(x+,t)P(x+,t) and P(y+,t)P(y+,t), and explain how their relative timing reveals the sign of ω0\omega_0.

  12. Derive the result of Example 4.5 by expanding ∣+z⟩|+z\rangle in the energy basis ∣±x⟩|\pm x\rangle, evolving the two components, and transforming back.

  13. Work through every branch of Example 4.6 rather than selecting only x−x-. Show that pooling the intermediate outcomes gives final statistics different from a protocol with no intermediate measurement.

  14. A Hamiltonian equals ℏΩσx/2\hbar\Omega\sigma_x/2 for a duration τ\tau and then ℏΩσy/2\hbar\Omega\sigma_y/2 for the same duration. Write the total evolution operator in the correct order. Repeat for the reversed pulse sequence and show that the results differ unless Ωτ\Omega\tau takes a special value.

  15. Derive equation (41) from the Schrödinger equation and its Hermitian conjugate.

  16. Use equation (42) to identify a conserved component of ⟨S⟩\langle\mathbf S\rangle in a constant magnetic field and connect it to energy conservation.

  17. Verify both pulse actions following equation (43) using explicit Pauli matrices.

  18. Calculate both pulse orders in Example 4.8 by matrix multiplication.

  19. Derive equation (49) from equation (48) and check δT=0,π,2π\delta T=0,\pi,2\pi.

  20. Insert an unread SzS_z measurement after the first Ramsey pulse and use density operators to show that both final outcomes have probability 1/21/2.

Selected exercise guidance

Use these answers only after making a complete attempt.

Exercise 2

The return amplitude is (1+e−iϵt/ℏ)/2(1+e^{-i\epsilon t/\hbar})/2, so the return probability is cos⁡2(ϵt/2ℏ)\cos^2(\epsilon t/2\hbar).

Exercise 5

For positive ω0\omega_0 under the chapter’s sign convention, the Bloch vector is (cos⁡ω0t,−sin⁡ω0t,0)(\cos\omega_0t,-\sin\omega_0t,0) and

P(y+,t)=1−sin⁡(ω0t)2.P(y+,t)=\frac{1-\sin(\omega_0t)}2.

It initially moves from +x+x toward −y-y.

Exercise 6

P(z−,t)=sin⁡2(∣ω∣t/2)P(z-,t)=\sin^2(|\omega|t/2), so the earliest certain flip occurs at t=π/∣ω∣t=\pi/|\omega|.

Exercise 19

At δT=0,π,2π\delta T=0,\pi,2\pi, the z+z+ probabilities are respectively 1,0,11,0,1; the z−z- probabilities are the complements.