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Time dependence in quantum mechanics describes how a prepared quantum state changes and thereby changes the probabilities of later measurements. For an isolated system, the Schrödinger picture assigns this evolution to a state vector $|\psi (t)⟩$, governed by the Time-dependent Schrödinger equationThe Hamiltonian is a self-adjoint operator; it has units of energy, while $\hslash$ has units of action, so $\hat{H}/\hslash$ has units of inverse time. For a particle with potential energy $V(\mathbf{r},t)$, this becomesGiven a suitable initial wavefunction and the physical boundary conditions, this first-order equation determines its subsequent propagation. Its linearity means that the evolution of a quantum superposition is the corresponding quantum superposition of evolved states.

For a real potential energy, this equation and its complex conjugate imply the local continuity equationHere $\rho$ is the probability density and $\mathbf{j}$ the probability current. Vanishing net boundary flux preserves wavefunction normalization, as required by the Born rule.

The time-evolution operator packages the solution for every initial state:Because ${\hat{H}}^{†}=\hat{H}$, differentiation givesTherefore $U^{†}U=I$: this is unitary time evolution, preserving inner products and all state norms. It is reversible, with $U(t,t_0{)}^{-1}=U(t_0,t)=U(t,t_0{)}^{†}$, and obeys the composition law $U(t_2,t_0)=U(t_2,t_1)U(t_1,t_0)$.

For a time-independent Hamiltonian, the solution is the operator exponentialIf the Hamiltonian varies with time, the analogous simple exponential of its integral is valid when $[\hat{H}(t),\hat{H}(t^{\prime })]=0$ for all relevant times. Otherwise time ordering is essential:The meaning is explicit in the first terms of the ordered series,the later-time operator stands on the left. In the position representation, the same propagation is expressed by the quantum-mechanical propagatorIts initial value is the Dirac delta function ${\delta }^3(\mathbf{r}-{\mathbf{r}}^{\prime })$.

A time-independent Hamiltonian has energy eigenstates satisfying $\hat{H}|n⟩=E_n|n⟩$. A single such initial state evolves asIt is a stationary state: its global phase changes, but its probability density and the distributions of time-independent observables do not. Its energy is sharp. Any quantum superposition entirely within one degenerate energy eigenspace also acquires one common global phase and is stationary. Stationarity does not require zero probability current; for instance, $u_n(\varphi )=e^{in\varphi }/\sqrt{2\pi }$ on the ring has a constant density and persistent circulation when $n\ne 0$.

An arbitrary normalized state can instead contain different energy eigenvalues:A continuous spectrum requires corresponding integrals. For the discrete case, an energy measurement gives $E_n$ with fixed probability $|c_n{|}^2$ (summed over degeneracies), but relative quantum phases change with time. ConsequentlyThe interference terms can oscillate at angular frequencies $(E_m-E_n)/\hslash$. For two populated energy levels, this supplies a characteristic period $2\pi \hslash /|E_m-E_n|$ when the interference term is nonzero. Thus fixed energy populations do not imply a stationary spatial distribution.

For a normalized state and an observable $\hat{A}(t)$, its expectation value isThis is the statistical mean over repeated preparations and measurements. In an eigenbasis of energy eigenstates for a time-independent Hamiltonian and a time-independent $\hat{A}$,Only matrix elements connecting different energies can generate these oscillations. If $[\hat{A},\hat{H}]=0$, its expectation value is constant for every initial state, provided it has no explicit time dependence.

Differentiating the expectation value and substituting the Schrödinger equation for both the bra and ket proves the general Ehrenfest theorem:Equivalently,These manipulations require the state to lie in the relevant operator domains. Taking $\hat{A}=\hat{H}$ gives $d⟨H⟩/dt=⟨{\partial }_t\hat{H}⟩$, so energy is conserved under a time-independent Hamiltonian.

For $\hat{H}={\hat{p}}^2/(2m)+V(\hat{x})$, the canonical commutation relation givesHence the particularly useful position-and-momentum form of Ehrenfest theorem isIt resembles Newton's second law, but the mean force generally differs from the force at the mean position. If a narrow wave packet samples a region where the force varies little, $⟨V^{\prime }(x)⟩\simeq V^{\prime }(⟨x⟩)$ gives approximate classical motion. For a quadratic potential energy this replacement is exact. In particular the quantum harmonic oscillator obeysThe centroid follows the classical harmonic oscillator, although this does not specify the full evolving wavefunction or its width.

The Heisenberg picture expresses the same physics by assigning evolution to observables instead:The expectation value is unchanged, and differentiation yields $d{\hat{A}}_H/dt=(i/\hslash )[{\hat{H}}_H,{\hat{A}}_H]+U^{†}({\partial }_t{\hat{A}}_S)U$. Thus state propagation, evolving expectation values, and the classical correspondence in Ehrenfest theorem are mutually consistent descriptions of the same unitary time evolution.

Here $V(x)$ is potential energy, $E$ is the stationary-state total energy eigenvalue, and $\psi (x)$ is its spatial wavefunction. Wavefunction normalization gives $\int |\psi {|}^{2}dx=1$, and $|\psi {|}^{2}dx$ is the probability of finding the particle in $dx$.

A bound state requires $-V_0<E<0$. Inside the well the equation is ${\psi }^{\prime \prime }=-k^2\psi$, whereas outside it is ${\psi }^{\prime \prime }=q^2\psi$, withThe ground state is even and has no node, selecting $\cos (kx)$ inside. Normalizability selects decaying, not growing, exterior exponentials. Continuity of $\psi$ and ${\psi }^{\prime }$ givesThe first excited state, if present, is odd: a sine inside and opposite-sign decaying tails outside. Matching gives $-k_1\cot (k_{1}a/2)=q_1>0$. On its first odd branch, $\pi /2<k_{1}a/2<\pi$, hence $k_{1}a>\pi$. Since $k_1^2<2m{V}_0/{\hslash }^2$, existence requiresThis is the first odd bound-state threshold of a square well. There is no excited bound state below that threshold; equality gives a non-normalizable zero-energy limiting state, not an extra bound state.

For the numerical well,The exterior probability of a symmetric finite-well state includes both tails:The threshold is $9.40\mathrm{eV}$, exceeding the well depth, so there is no excited bound state. The rounded supplied coefficients integrate to $0.9973$ rather than exactly one; this rounding does not change the quoted probability precision materially.

Equation and interpretation. The supplied equation is the time-independent Schrödinger equation for a nonrelativistic particle with mass $m$ in a prescribed potential energy $V(x)$. Equivalently,It is an eigenvalue problem for the Hamiltonian operator. A stationary energy state has full wavefunction $\Psi (x,t)=\psi (x)e^{-iEt/\hslash }$. By the Born rule, $|\psi (x){|}^{2}dx$ is the probability of finding the particle in a small interval $dx$, with wavefunction normalization ${\int }_{-\infty }^{\infty }|\psi {|}^{2}dx=1$.

Infinite barriers. Infinite exterior potential energy excludes any finite-energy probability outside the interval. The infinite square well consequently has $\psi =0$ outside and the hard-wall boundary conditionsThe interior wavefunction must meet the zero exterior amplitude continuously. Its derivative need not be continuous across an infinite wall; imposing both zero value and zero derivative would eliminate every nonzero interior solution.

Ground state. Inside the well $V=0$, so ${\psi }^{\prime \prime }+k^2\psi =0$, with $k=\sqrt{2mE}/\hslash$. Its general solution is $A\sin kx+B\cos kx$. The left wall gives $B=0$, and the right wall gives $ka=n\pi$ for $n=1,2,\dots$. Thus the discrete energy eigenvalues are $E_n=n^2{\pi }^2{\hslash }^2/(2m{a}^2)$. The smallest, $n=1$, is the ground state. Sinceits normalized wavefunction, choosing an irrelevant overall phase to make it positive inside, is

Finite barriers. For a finite step and constant particle mass, both $\psi$ and ${\psi }^{\prime }$ are continuous at $x=0,a$. Wavefunction matching at a finite potential step follows by integrating the Schrödinger equation across a vanishingly small neighborhood of the step: a bounded potential cannot generate a finite jump in ${\psi }^{\prime }$. The bound-state exterior solutions decay rather than vanish identically:Normalizability excludes the growing exterior exponentials. The equivalent interior boundary conditions are ${\psi }^{\prime }(0)=\kappa \psi (0)$ and ${\psi }^{\prime }(a)=-\kappa \psi (a)$; neither boundary value is zero for the nontrivial ground state.

The ground state of a finite square well remains symmetric about $a/2$ and has no nodes. It bends smoothly into exponential tails at both walls, extending over a larger region than the infinite-well state. Its maximum after normalization is lower for the deep well considered here. When $V_w\gg E$, the penetration length $1/\kappa$ is short, so the two shapes are close except near the walls and in the exterior tails.

The finite curve is an illustrative exact matched solution with $V_w=10E_{1,\infty }$; no numerical wall height is specified by the question.

Energy comparison. The finite barriers relax the confinement, allowing a less rapidly varying interior wavefunction and therefore smaller kinetic energy. More explicitly, the even interior solution is proportional to $\cos [k(x-a/2)]$, and matching to the tails gives $k\tan (ka/2)=\kappa$. The lowest root lies at $0<ka<\pi$, while the infinite well has $ka=\pi$. HenceAs $V_w\to \infty$, the tails disappear and the finite-well energy approaches the infinite-well value from below. This comparison uses the same zero of potential energy inside both wells.

The time-independent Schrödinger equation is the energy eigenvalue equation $\hat{H}\psi =E\psi$ for a particle of mass $m$. The Hamiltonian operator is the sum of the kinetic operator $-({\hslash }^2/2m)d^2/d{x}^2$ and the prescribed potential energy $V(x)$. Here $\hslash$ is the reduced Planck constant. A corresponding stationary state is $\Psi (x,t)=\psi (x)e^{-iEt/\hslash }$. The Born rule identifies $|\Psi {|}^2=|\psi {|}^2$ as probability density for a state with wavefunction normalization $\int |\Psi {|}^{2}dx=1$; integrating it over an interval gives a position probability. A plane wave scattering state is not a normalizable wavefunction on the whole line, but its probability currents give the reflection and transmission fractions of an incident wave packet.

There is a notation discrepancy in the sources: the original PDF prints an unbarred $h^2$ in the kinetic term, whereas the local TeX uses ${\hslash }^2$. The standard physical equation uses the reduced Planck constant $\hslash =h/(2\pi )$, where $h$ is the Planck constant; that convention is used below. Reading the printed $h$ literally as the Planck constant would scale all lengths in this model by $2\pi$ relative to the standard answers, but would leave the amplitude ratios unchanged.

For $E>V_0$, both sides allow oscillatory wavefunctions. A classical particle always crosses the potential step and slows because its kinetic energy falls from $E$ to $E-V_0$. In quantum mechanics there is generally both reflection and transmission even though the particle is above the step. Define the positive wavenumbersWith no wave incident from the right, writeA finite potential step with constant mass makes both the wavefunction and its first derivative continuous. The two boundary conditions at $x=0$ areSolving gives the reflected and transmitted wavefunctionsFor the specified electron energies, $q/k=\sqrt{10/50}=1/\sqrt{5}$, so the relative probability amplitudes areThe transmitted probability amplitude exceeding one is compatible with conservation of quantum probability, since the outgoing speed is smaller. In fact the probability current $j=(\hslash /m)\mathrm{Im}({\psi }^{\ast }{\psi }^{\prime })$ givesThese are the quantum reflection probability and transmission probability, which must be distinguished from the requested relative amplitudes.

Wavefunction normalization cancels in the ratio of integrals:A normalized version of the specified wavefunction is $\sqrt{3}(a+ix)/(2a^{3/2})$ on its support.

For a normalized orbital $\int d^{2}r|\varphi {|}^2=1$, the symmetric Hartree product state and its equivalent Fock space form areThere are exactly $N(N-1)/2$ interacting pairs, so the expectation value of the grand Hamiltonian is the functionalAt fixed $N$ the term $-\mu N$ is constant. Enforce wavefunction normalization separately by varying ${\mathcal{E}}_{\mu }-N\eta (\int |\varphi {|}^2-1)$ with respect to ${\varphi }^{\ast }$. The resulting stationary Gross–Pitaevskii equation for the normalized orbital isThe Lagrange multiplier $\eta$ enforces the norm; fixed-$N$ variation cannot identify it with the independently inserted chemical potential merely by differentiating the constant $-\mu N$.

For the standard large-$N$ convention put $\Psi =\sqrt{N}\varphi$, so $n=|\Psi {|}^2$ and $\int n=N$, and replace $N-1$ by $N$. Varying the resulting grand energy functionalwith unrestricted $\Psi$ givesEquivalently, at fixed $N$ this same $\mu$ is chosen as the normalization Lagrange multiplier. This is the chemical potential convention used below. The contact interaction coupling $g$ has dimensions of energy times area in two dimensions.

The time-independent Schrödinger equation is the energy eigenvalue equation for the Hamiltonian operator:Here $\hslash$ is the reduced Planck constant. A corresponding stationary wavefunction evolves as $\Psi (x,t)=\psi (x)e^{-iEt/\hslash }$, which follows by substitution in the Time-dependent Schrödinger equation. Its position probability density is time independent because the time factor has unit modulus. Physical energy eigenstates must also satisfy the system's boundary conditions; for a bound state, wavefunction normalization requires ${\int }_{-\infty }^{\infty }|\psi (x){|}^{2}dx=1$.

Write $\rho =a\sqrt{2m{V}_0}/\hslash >0$. On the first tangent branch, $0<\beta <\pi /2$, the matching relations are equivalent toThe function $g(\beta )=\beta /\cos \beta$ is continuous and strictly increasing there:The intermediate value theorem therefore gives a unique first-branch root for every $\rho >0$. At this root $\beta <\rho$ and $\alpha =\beta \tan \beta >0$, so the energy eigenvalueobeys $-V_0<E<0$. This proves the even bound state in every attractive square well result.

To verify all the requested properties, take the resulting even wavefunction with exterior tails written in terms of their boundary values:The matching equation makes both the values and first derivatives agree at the endpoints. The exterior tails are square-integrable because $k>0$, and the interior interval is finite. More explicitly,so choosing $B$ as the positive inverse square root of the bracket gives wavefunction normalization. Thus an even, continuously differentiable, normalizable stationary solution always exists, however small the positive depth.

For brevity write $\gamma =mKZ/{\hslash }^2$. With the physical indicial root $c=\ell +1$, substitute $f={\sum }_{n\ge 0}{a}_n{r}^{n+\ell +1}$ into the equation from part (i). The coefficient of $r^{n+\ell }$ isThe indicial equation has already canceled the still lower power $r^{\ell -1}$. Rearranging gives the recurrence relationIts denominator is $(n+1)(n+2\ell +2)>0$ for every $n\ge 0$.

To impose wavefunction normalization at infinity, first suppose that the series never terminates. ThenThis is the exponential-series growth associated with $e^{2\alpha r}$, which would overwhelm the factor $e^{-\alpha r}$ in $\psi$. A direct lower-bound argument makes the conclusion precise. All sufficiently late recurrence ratios are real and positive, so after a common global phase choice the tail coefficients have one sign. For any $0<\eta <\alpha$, there is an index $N$ such thatInduction then bounds the tail below by a positive multiple ofThe finitely many earlier terms form a polynomial and cannot cancel this exponential growth. Thus $|\psi |=r^{-1}{e}^{-\alpha r}|f|$ grows at least as a positive multiple of $r^{\ell }{e}^{(\alpha -\eta )r}$ for large $r$, contradicting wavefunction normalization. This proves that the regular series must terminate.

Since the denominator never vanishes, termination requires the numerator to vanish at some nonnegative integer $n$:Then $a_{n+1}=0$ and every later coefficient is zero. Consequently $f$ is a polynomial of degree $n+\ell +1$, with a factor $r^{\ell +1}$; equivalently,where $P_n$ has degree $n$. This is series-termination quantization of the Coulomb radial equation. If $N_{\mathrm{p}}=n+\ell +1$ denotes the principal quantum number, the associated energy eigenvalues areHere $n$ counts the degree of the remaining radial polynomial; it is not the principal quantum number itself.

Apply the Frobenius method at the origin. The lowest power in $f^{\prime \prime }-\ell (\ell +1)f/r^2$ is $r^{c-2}$, with coefficientThe terms $-2\alpha f^{\prime }$ and $2mKZf/({\hslash }^{2}r)$ start at power $r^{c-1}$ and therefore cannot cancel a nonzero $r^{c-2}$ coefficient. Because $a_0\ne 0$, the indicial equation isIts roots are $c=\ell +1$ and $c=-\ell$. Since $\psi =r^{-1}f{e}^{-\alpha r}$, their leading behaviors are respectively $\psi \sim r^{\ell }$ and $\psi \sim r^{-\ell -1}$. The physical choice isThis is the Coulomb radial origin condition. For $\ell \ge 1$, the other branch is not even locally normalizable: its radial probability integral behaves as ${\int }_0^{\epsilon }{r}^2{r}^{-2\ell -2}dr={\int }_0^{\epsilon }{r}^{-2\ell }dr$, which diverges.

For $\ell =0$, the singular behavior $1/r$ is locally square-integrable with the measure $r^{2}dr$, so local wavefunction normalization alone would not reject it. The ordinary three-dimensional Coulomb potential problem additionally requires the regular boundary condition $u(0)=0$. A $1/r$ branch violates that condition and has divergent kinetic energy integral ${\int }_0^{\epsilon }{r}^2|{\partial }_r(1/r){|}^{2}dr={\int }_0^{\epsilon }{r}^{-2}dr$. Thus it is excluded from the physical energy domain as well. The regular choice gives $u\sim r^{\ell +1}$ in every case.

The smallest energy eigenvalue in part (iii) occurs at the smallest possible principal quantum number, $N_{\mathrm{p}}=1$. Since $n,\ell \ge 0$, this forces $n=0$ and $\ell =0$. Therefore $f=a_{0}r$, andFor the spherically symmetric ground state, the full three-dimensional wavefunction normalization uses $d^{3}x=r^{2}drd\Omega$. Integrating over the solid angle givesPut $R=2{\alpha }_{0}r$ and use the supplied factorial integral:Thus $|a_0{|}^2={\alpha }_0^3/\pi$. Choosing the positive global phase convention givesThis is the radial normalization of the hydrogen ground state convention in which the angular factor is absorbed into the spherically symmetric function. If instead one writes $\Psi =R(r)Y_{00}$ with the normalized spherical harmonic $Y_{00}=1/\sqrt{4\pi }$, then $R(r)=2{\alpha }_0^{3/2}{e}^{-{\alpha }_{0}r}$. Both conventions describe the same normalized three-dimensional quantum state.

Inside the infinite square well, the Schrödinger equation and Dirichlet boundary conditions areThe wavefunction vanishes outside the box. These walls constrain its values, not its first derivatives: requiring both to vanish at an endpoint would eliminate all the nonzero stationary solutions.

For a nonzero separated solution, separation of variables givesThe last equation is the time-independent Schrödinger equation. Its energy eigenvalue is real. Multiplication by ${\psi }^{\ast }$ and integration by parts, with the endpoint values zero, givesEquality would force $\psi$ to be constant and hence zero, so a nonzero energy eigenstate has $E>0$. Writing $k=\sqrt{2mE}/\hslash$, the general solution is $A\sin kx+B\cos kx$. The left wall gives $B=0$; the right gives $\sin ka=0$. Negative integers reproduce the same functions up to a constant, and $n=0$ gives the zero function, leaving $k=n\pi /a$ for $n=1,2,\dots$.

Finally ${\int }_0^a{\sin }^2(n\pi x/a)dx=a/2$. Thus wavefunction normalization with positive coefficient givesAn arbitrary constant global phase has no effect on the quantum state.

The spatial quantum phase has unit modulus. Thus the probability density and total probability areThe exterior contributes zero. This establishes wavefunction normalization, although the spatial quantum phase means the state is not the ground energy eigenstate.

Put $\gamma =2m\hslash \omega$. If ${\psi }_n$ is a normalized energy eigenstate at $E_n$, the factorization from part (a) givesIt follows inductively that $v_n=(a_{+}{)}^n{\psi }_0$ has squared norm ${\gamma }^{n}n!$. The commutator with $H$ establishes its energy eigenvalue at each step. Henceis normalized and has $E_n=(n+\frac{1}{2})\hslash \omega$. Distinct levels are orthogonal because $H$ is a self-adjoint operator. In particular,

To decompose the specified initial wavefunction, retain this exact phase convention for the creation and annihilation operators. Their difference givesSince $a_{-}{\psi }_0=0$ and $a_{-}{a}_{+}{\psi }_0=\gamma {\psi }_0$,This quadratic excitation of an oscillator ground state, $\Psi (x,0)=C_0^{-1}{X}^2{\psi }_0$, contains only the $n=0$ and $n=2$ energy eigenstates. The printed initial function has an unspecified overall normalization, so the Born rule requires division by its squared norm. After wavefunction normalization the state isThe minus sign is consistent with the paper's convention: its $a_{+}$ is $i$ times the usual real-coordinate raising operator multiplied by $\sqrt{\gamma }$, so its ${\psi }_2$ has the opposite sign to the usual real second harmonic oscillator eigenfunction. The energy measurement probabilities are independent of this choice of phase.

Therefore the complete answer isEvery other energy has probability zero. At any later time the two coefficients only acquire their separate dynamical phases, so these probabilities remain the same. A direct check of the normalization isThis also confirms the factor of three in the squared norm of the two-component expansion.

For a momentum eigenstate with eigenvalue $p$, the equation $-i\hslash {\psi }^{\prime }=p\psi$ has solution $\psi (x)=C{e}^{ipx/\hslash }$. The periodic boundary condition imposes $e^{2\pi ip/\hslash }=1$, so $p/\hslash \in \mathbb{Z}$. The wavefunction normalization gives $1=2\pi |C{|}^2$. Choosing a convenient global phase yieldsThese momentum eigenstates form an orthonormal basis, the Fourier basis for the particle on a circle:Here ${\delta }_{nk}$ is the Kronecker delta.

For a free particle, the Hamiltonian operator is $H=P^2/(2m)$, where $P=-i\hslash d/dx$ is the momentum operator. The time-independent Schrödinger equation is thereforeThe full stationary state is $\Psi (x,t)=e^{-iEt/\hslash }\psi (x)$. The periodic boundary condition identifies $x$ and $x+2\pi$, giving a particle on a circle with wavefunction normalization over one period.

The identity ${\cos }^{2}x=\frac{1}{2}+\frac{1}{4}{e}^{2ix}+\frac{1}{4}{e}^{-2ix}$ gives the momentum eigenstate expansionUsing the orthonormal basis from part (a), the wavefunction normalization isHence $|A|=2/\sqrt{3\pi }$. The wavefunction normalization leaves a global phase free; the positive real choice used in the requested expansion givesThe two nonzero eigenvalues of the momentum operator have the same energy eigenvalue $E_{\star }=2{\hslash }^2/m$. Under unitary time evolution, their coefficients acquire the same dynamical phase. With $\Omega =E_{\star }/\hslash =2\hslash /m$,At $t=0$, $1+\cos (2x)=2{\cos }^{2}x$ recovers the initial wavefunction. Its probability density, useful below, is