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For a nonzero quantum state $\psi$ and a self-adjoint operator $A$, the expectation value and standard deviation of its measurement areThe squared deviation is also called the variance of the observable. All displayed products are understood on quantum states for which the relevant moments exist. Self-adjointness gives $\overline{⟨\psi ,A\psi ⟩}=⟨A\psi ,\psi ⟩=⟨\psi ,A\psi ⟩$, so $a$ is real. Expanding the squared norm gives the variance expression. A norm is nonnegative and is zero exactly for the zero vector, hence ${\Delta }_{\psi }(A)=0$ precisely when $A\psi =a\psi$. Thus zero dispersion is equivalent to being an eigenstate.

For bounded $H$, the operator exponential is the norm-convergent power seriesFor a general unbounded self-adjoint Hamiltonian operator, the spectral theorem defines the same notation byThis definition does not require the power series to converge on every quantum state. complex conjugation of the spectral multiplier gives $U_t^{\ast }=U_{-t}$, and multiplication of the phases gives $U_{-t}{U}_t=I$. Thus $U_t$ is unitary, preserves the quantum state norm, and has $U_0=I$.

For initial data in the domain of $H$, differentiating the spectral expression yields ${\partial }_t{U}_t{\psi }_0=-(i/\hslash )H{U}_t{\psi }_0$. Consequentlysolves the Schrödinger equation with the prescribed initial quantum state. Uniqueness follows by differentiating $U_{-t}{\psi }_t$: the two terms cancel, leaving the constant ${\psi }_0$.

In the two-dimensional energy basis, expand the initial quantum state as ${\psi }_0=c_1{\Psi }_1+c_2{\Psi }_2$. Each energy eigenvector receives its own phase under the operator exponential, givingThis is the general solution because every initial vector has a unique basis expansion.

In that orthonormal basis the other observable has the real symmetric matrixIts conjugate transpose equals itself, so it is self-adjoint. Also $A^2=I$ and $\mathrm{tr}A=0$, giving eigenvalues $+1$ and $-1$. Direct substitution gives the normalized orthogonal eigenvectorsAn irrelevant global phase may multiply either vector. With the chosen lower eigenstate initially,The Born rule says that the probability for the higher eigenstate is $|⟨v_{+},{\psi }_t⟩{|}^2$. Its amplitude is $\sin \alpha \cos \alpha (e^{-it{E}_2/\hslash }-e^{-it{E}_1/\hslash })$. Using $|e^{-iu}-e^{-iv}{|}^2=4{\sin }^2((u-v)/2)$ givesThis is the transition probability for a rotated two-level observable. Its time dependence comes from the relative phase between two energy eigenstates. If their energies coincide, or if the measured observable has the energy eigenvectors as its eigenvectors, this transition probability is zero at all times.

In the scalar two-particle model, the fermionic exchange symmetry and bosonic exchange symmetry conditions areFor particles with spin, exchange acts on all their labels; the stated coordinate-only model fixes the spatial symmetry sector. Define $S\Psi (x_1,x_2)=\Psi (x_2,x_1)$. Equal masses make the kinetic operator invariant under exchange, and the assumed potential is invariant too, so $HS=SH$. Therefore $H\Psi =E\Psi$ implies $H(S\Psi )=E(S\Psi )$. The componentsare respectively symmetric and antisymmetric eigenfunctions whenever nonzero. Their sum is the original nonzero quantum state, so at least one is nonzero. An eigenspace may contain both sectors if the energy is degenerate.

The normal modes of two harmonically coupled identical particles provide the separation. The coordinate transformation to $y_{+},y_{-}$ is orthogonal, with absolute Jacobian one. Exchanging the particles leaves $y_{+}$ fixed and changes $y_{-}$ to $-y_{-}$. Hence bosonic quantum states are even and fermionic quantum states odd in the relative coordinate. The chain rule givesAlso $x_1^2+x_2^2=y_{+}^2+y_{-}^2$ and $(x_1-x_2{)}^2=2y_{-}^2$. Combining the two trapping potentials with the interaction therefore gives the separated Hamiltonian operatorThese are independent oscillators of frequencies $\omega$ and $\omega \cos \alpha$. Both frequencies are positive in the stated range. Their product eigenstates have energiesThe parity of an oscillator level is $(-1{)}^n$. Consequently bosons allow even $n_{-}$ and fermions odd $n_{-}$, while $n_{+}$ is unrestricted.

The bosonic ground state uses $n_{+}=n_{-}=0$, and the fermionic ground state uses $n_{+}=0,n_{-}=1$. The oscillator length in the relative mode isUsing the normalized Gaussian for each mode givesIndeed ${\varphi }_{\tau }(y)=\sqrt{2}y{\psi }_{\tau }(y)/\tau$ by differentiating the Gaussian, so it is the normalized odd first excited state. The ground energies are $E_{\mathrm{B}}=\hslash \omega (1+\cos \alpha )/2$ and $E_{\mathrm{F}}=\hslash \omega (1+3\cos \alpha )/2$.

Choose normalized factors for a normalized product quantum state; this can always be done by reciprocal rescaling of its factors. Since the coordinate Jacobian has absolute value one,If the supplied factors are not individually normalized, the general expression has an additional factor $\Vert \psi {\Vert }^2$; choosing normalized factors is the convention in the displayed formula.

For the ground states, put $\rho (y)=|{\psi }_{\tau }(y){|}^2=e^{-y^2/{\tau }^2}/(\sqrt{\pi }\tau )$. Then $|{\varphi }_{\tau }(y){|}^2=2y^2\rho (y)/{\tau }^2$ and ${\rho }^{\prime }=-2y\rho /{\tau }^2$. Thus, for differentiable $f$ with suitable Gaussian integrability and vanishing boundary terms,This is integration by parts, and every polynomial satisfies the required endpoint conditions. The relative-coordinate moments in even and odd oscillator ground states follow by substituting $f(y)=y^n$:For odd $n$, both expectations vanish by parity, so this is an equality of zeros rather than an increase in signed mean separation. The even moments show the physical difference. In particular ${\mathbb{E}}_{\mathrm{B}}[y_{-}^2]={\tau }^2/2$ and ${\mathbb{E}}_{\mathrm{F}}[y_{-}^2]=3{\tau }^2/2$, so the fermionic root-mean-square particle separation is $\sqrt{3}$ times the bosonic value. The fermionic probability density vanishes at coincidence $y_{-}=0$, expressing Pauli exclusion principle in this spatial symmetry sector. This is an exchange constraint on the wave function, not an additional classical force. As $\alpha$ approaches $\pi /2$, the relative oscillator softens and its width diverges; the excluded endpoint would no longer have this normalizable oscillator ground state.

Use an expansion for the eigenstate continuing the nondegenerate level, with intermediate normalization $⟨{\psi }_0,\psi (ϵ)⟩=1$:Insert these expressions into the eigenvalue equation. At first order,Taking the inner product with ${\psi }_0$ eliminates the left side by self-adjointness. ThusFor $j\ne 0$, projection onto ${\psi }_j$ instead givesAt second order, projecting the eigenvalue equation onto ${\psi }_0$ gives $E^{(2)}=⟨{\psi }_0,H^{\prime }\chi ⟩$. Expand $\chi$ in the orthonormal energy basis and use self-adjointness of $H^{\prime }$:Nondegeneracy ensures the denominators for this level do not vanish; convergence and validity of the expansion are among the assumed perturbation-theory hypotheses.

For the cosine perturbation of the ground level in a one-dimensional box, write $u=\pi x/a$. The product-to-sum identity givesso, with the given common normalization of the sine eigenfunctions,The diagonal matrix element is $-ϵ/2$, and the only nonzero off-diagonal matrix element out of the ground state is $⟨{\varphi }_3,V{\varphi }_1⟩=ϵ/2$. Let $E_{\mathrm{box}}={\pi }^2{\hslash }^2/(2m{a}^2)$. Since ${\mathcal{E}}_3=9E_{\mathrm{box}}$, the ground energy isThe second-order term is negative, as expected for a nondegenerate ground level: every excited-quantum state denominator is negative. The first-order shift is also negative for positive $ϵ$, because the ground-quantum state density is largest near the center, where this perturbing potential is negative.

Let $U(t)=e^{-iHt/\hslash }$ and take an observable with no explicit time dependence. In the Schrödinger picture, ${\psi }_S(t)=U(t){\psi }_0$ and $A_S=A$. In the Heisenberg picture, ${\psi }_H={\psi }_0$ and $A_H(t)=U(t{)}^{†}AU(t)$. For the interaction picture choose a time-independent splitting $H=H_0+V$, put $U_0=e^{-i{H}_{0}t/\hslash }$, and defineThen $i\hslash {\dot{\psi }}_I=V_I{\psi }_I$ and ${\dot{A}}_I=(i/\hslash )[H_0,A_I]$. Unitarity gives the identical expectation in all three descriptions:Different choices of the split interpolate between pictures; $H_0=H$ makes the state constant, while $H_0=0$ gives the Schrödinger description.

Differentiate $U^{†}AU$ to obtain the Heisenberg equation of motionFor an explicitly time-dependent observable there is additionally $U^{†}({\partial }_{t}A)U$. Thus $H_H=H$ is constant. In a normalized energy eigenstate, $⟨[H,A_H]⟩=E⟨A_H⟩-E⟨A_H⟩=0$, so the expectation of its Heisenberg derivative vanishes whenever the products are defined.

For the harmonic oscillator, the canonical commutator givesThe last identity follows from the operator product rule without commuting $X$ and $P$. Although $XP$ is not itself self-adjoint, the same calculation can be applied to the self-adjoint dilation observable $(XP+PX)/2$ and gives the same derivative.

Stationarity of the three expectations gives $⟨P⟩=⟨X⟩=0$ and $⟨P^2⟩=m^2{\omega }^2⟨X^2⟩$. Substitution into $E=⟨P^2⟩/(2m)+m{\omega }^2⟨X^2⟩/2$ yields the quantum virial theoremThe vanishing means make the variances equal to the second moments, soThis satisfies the position-momentum Heisenberg uncertainty relation, with equality only for the ground state.

For two spin one-half particles, $s_1^2=s_2^2=3{\hslash }^2/4$. Squaring $\mathbf{S}={\mathbf{s}}_1+{\mathbf{s}}_2$ givesTake $a,b$ real so that $f$ is Hermitian. Since $[S^2,S_z]=0$, the displayed polynomial implies $[f,S^2]=[f,S_z]=0$. There is a common orthonormal eigenbasis, so all three observables can be simultaneously certain in a common eigenstate. Commutation does not mean that every quantum superposition has definite values of all three.

Write $\Psi =(|\downarrow \uparrow ⟩+|\uparrow \downarrow ⟩)/\sqrt{2}$. Each term has cancelling $z$ components, so $S_z\Psi =0$. In the formula for $S^2$, the first three terms contribute $(3/2-1/2){\hslash }^2\Psi ={\hslash }^2\Psi$. The two ladder products exchange the two terms and contribute another ${\hslash }^2\Psi$. ThereforeThis spin state is symmetric; the accompanying spatial state must be antisymmetric for two electrons. A labelled product $|{\downarrow }_1{\uparrow }_2⟩$ alone is not an eigenstate of spin exchange: its exchanged vector is orthogonal to it. Thus it cannot supply a definite exchange symmetry when multiplied by a fixed symmetric spatial factor.

This does not prohibit opposite spins in different spatial orbitals. For example, with orthonormal orbitals ${\varphi }_a,{\varphi }_b$, the Slater determinantis a valid antisymmetric two-electron state. What fails is treating persistent particle labels as physically distinguishable identities without the required antisymmetrization.

For a conditional spin measurement of identical fermions addressing the $z$ component in one spatial mode, the Born rule givesConditioned on this result, the mode spin state is $|{\uparrow }_a{\downarrow }_b⟩$; the other outcome produces $|{\downarrow }_a{\uparrow }_b⟩$. The spin product is not a spin-exchange eigenstate. The measurement has selected an addressed mode and recorded an outcome, so this conditional spin description distinguishes the measured subsystem.

The full electron wavefunction still obeys fermionic exchange symmetry. For example, the conditional spin-up outcome in spatial mode $a$ is represented in particle coordinates byIt is antisymmetric under full particle exchange. Thus the loss of a definite symmetry of the conditional spin product does not mean that measurement turns identical electrons into distinguishable particles. If the outcome is discarded, the mode spin state is instead the equal mixture of the two opposite-spin products. The measurement must specify which spatial mode is addressed for the conditional statement to be operationally meaningful.

The spherical harmonics satisfyCommuting $L^2$ or $L_z$ past $L_{\pm }$ therefore givesFor a nonzero result these are the eigenvalue equations with unchanged $l$ and shifted magnetic quantum number. Taking the squared norm, using $L_{\mp }{L}_{\pm }=L^2-L_z^2\mp \hslash L_z$, fixes the conventional coefficient:At the appropriate endpoint the coefficient is zero. The zero vector is not itself an eigenstate.

The linear confinement correction to Coulomb bound states uses $H^{\prime }=br$, and its first-order energy correction in a normalized Coulomb eigenstate is $b⟨r⟩$. Replace $a_0$ by $a_q$ in the hydrogen wavefunctions. The normalized spherical harmonics remove the angular integral, leavingFor $1s$, the integral of $r^3{e}^{-2r/a_q}$ yieldsFor $2s$, put $u=r/a_q$ and square the full radial polynomial, including its cross term:For $2p$, the same calculation givesConsequently the first two Coulomb levels become, to first order,Thus the second level splits into a singlet orbital level and a triply degenerate orbital level, with $E_{2s}-E_{2p}=b{a}_q+O(b^2)$. For the confining sign $b>0$, $2p$ lies lower than $2s$: its smaller mean radius gives the smaller positive correction. The expansion assumes these corrections and the induced couplings to other principal shells are small compared with the relevant Coulomb energy gaps; $b{a}_q^2/a\ll 1$ is the governing small parameter for fixed low $n$.

The unperturbed $n=2$ level is degenerate. The useful point is that a central perturbation is already diagonal within its usual orbital eigenbasis:Angular orthogonality removes the possible mixing of $2s$ and $2p$, and also the mixing of different magnetic sublevels. Therefore the matrix required by degenerate perturbation theory needs no further diagonalization: its diagonal entries are precisely the expectation values above. It would be incorrect to justify the calculation by claiming that the unperturbed spectrum was nondegenerate.

For $b=0$ the energy needs only $n$. For a nonzero central confinement term the energy generally needs $n,l$, but remains independent of $m$. The magnetic quantum number is still needed to specify an individual orbital eigenstate, rather than just its energy.

Let $U(t)=e^{-iHt/\hslash }$ and take an observable with no explicit time dependence. In the Schrödinger picture, ${\psi }_S(t)=U(t){\psi }_0$ and $A_S=A$. In the Heisenberg picture, ${\psi }_H={\psi }_0$ and $A_H(t)=U(t{)}^{†}AU(t)$. For the interaction picture choose a time-independent splitting $H=H_0+V$, put $U_0=e^{-i{H}_{0}t/\hslash }$, and defineThen $i\hslash {\dot{\psi }}_I=V_I{\psi }_I$ and ${\dot{A}}_I=(i/\hslash )[H_0,A_I]$. Unitarity gives the identical expectation in all three descriptions:Different choices of the split interpolate between pictures; $H_0=H$ makes the state constant, while $H_0=0$ gives the Schrödinger description.

Differentiate $U^{†}AU$ to obtain the Heisenberg equation of motionFor an explicitly time-dependent observable there is additionally $U^{†}({\partial }_{t}A)U$. Thus $H_H=H$ is constant. In a normalized energy eigenstate, $⟨[H,A_H]⟩=E⟨A_H⟩-E⟨A_H⟩=0$, so the expectation of its Heisenberg derivative vanishes whenever the products are defined.

For the harmonic oscillator, the canonical commutator givesThe last identity follows from the operator product rule without commuting $X$ and $P$. Although $XP$ is not itself self-adjoint, the same calculation can be applied to the self-adjoint dilation observable $(XP+PX)/2$ and gives the same derivative.

Stationarity of the three expectations gives $⟨P⟩=⟨X⟩=0$ and $⟨P^2⟩=m^2{\omega }^2⟨X^2⟩$. Substitution into $E=⟨P^2⟩/(2m)+m{\omega }^2⟨X^2⟩/2$ yields the quantum virial theoremThe vanishing means make the variances equal to the second moments, soThis satisfies the position-momentum Heisenberg uncertainty relation, with equality only for the ground state.

In the scalar two-particle model, the fermionic exchange symmetry and bosonic exchange symmetry conditions areFor particles with spin, exchange acts on all their labels; the stated coordinate-only model fixes the spatial symmetry sector. Define $S\Psi (x_1,x_2)=\Psi (x_2,x_1)$. Equal masses make the kinetic operator invariant under exchange, and the assumed potential is invariant too, so $HS=SH$. Therefore $H\Psi =E\Psi$ implies $H(S\Psi )=E(S\Psi )$. The componentsare respectively symmetric and antisymmetric eigenfunctions whenever nonzero. Their sum is the original nonzero quantum state, so at least one is nonzero. An eigenspace may contain both sectors if the energy is degenerate.

The normal modes of two harmonically coupled identical particles provide the separation. The coordinate transformation to $y_{+},y_{-}$ is orthogonal, with absolute Jacobian one. Exchanging the particles leaves $y_{+}$ fixed and changes $y_{-}$ to $-y_{-}$. Hence bosonic quantum states are even and fermionic quantum states odd in the relative coordinate. The chain rule givesAlso $x_1^2+x_2^2=y_{+}^2+y_{-}^2$ and $(x_1-x_2{)}^2=2y_{-}^2$. Combining the two trapping potentials with the interaction therefore gives the separated Hamiltonian operatorThese are independent oscillators of frequencies $\omega$ and $\omega \cos \alpha$. Both frequencies are positive in the stated range. Their product eigenstates have energiesThe parity of an oscillator level is $(-1{)}^n$. Consequently bosons allow even $n_{-}$ and fermions odd $n_{-}$, while $n_{+}$ is unrestricted.

The bosonic ground state uses $n_{+}=n_{-}=0$, and the fermionic ground state uses $n_{+}=0,n_{-}=1$. The oscillator length in the relative mode isUsing the normalized Gaussian for each mode givesIndeed ${\varphi }_{\tau }(y)=\sqrt{2}y{\psi }_{\tau }(y)/\tau$ by differentiating the Gaussian, so it is the normalized odd first excited state. The ground energies are $E_{\mathrm{B}}=\hslash \omega (1+\cos \alpha )/2$ and $E_{\mathrm{F}}=\hslash \omega (1+3\cos \alpha )/2$.

Choose normalized factors for a normalized product quantum state; this can always be done by reciprocal rescaling of its factors. Since the coordinate Jacobian has absolute value one,If the supplied factors are not individually normalized, the general expression has an additional factor $\Vert \psi {\Vert }^2$; choosing normalized factors is the convention in the displayed formula.

For the ground states, put $\rho (y)=|{\psi }_{\tau }(y){|}^2=e^{-y^2/{\tau }^2}/(\sqrt{\pi }\tau )$. Then $|{\varphi }_{\tau }(y){|}^2=2y^2\rho (y)/{\tau }^2$ and ${\rho }^{\prime }=-2y\rho /{\tau }^2$. Thus, for differentiable $f$ with suitable Gaussian integrability and vanishing boundary terms,This is integration by parts, and every polynomial satisfies the required endpoint conditions. The relative-coordinate moments in even and odd oscillator ground states follow by substituting $f(y)=y^n$:For odd $n$, both expectations vanish by parity, so this is an equality of zeros rather than an increase in signed mean separation. The even moments show the physical difference. In particular ${\mathbb{E}}_{\mathrm{B}}[y_{-}^2]={\tau }^2/2$ and ${\mathbb{E}}_{\mathrm{F}}[y_{-}^2]=3{\tau }^2/2$, so the fermionic root-mean-square particle separation is $\sqrt{3}$ times the bosonic value. The fermionic probability density vanishes at coincidence $y_{-}=0$, expressing Pauli exclusion principle in this spatial symmetry sector. This is an exchange constraint on the wave function, not an additional classical force. As $\alpha$ approaches $\pi /2$, the relative oscillator softens and its width diverges; the excluded endpoint would no longer have this normalizable oscillator ground state.

Use an expansion for the eigenstate continuing the nondegenerate level, with intermediate normalization $⟨{\psi }_0,\psi (ϵ)⟩=1$:Insert these expressions into the eigenvalue equation. At first order,Taking the inner product with ${\psi }_0$ eliminates the left side by self-adjointness. ThusFor $j\ne 0$, projection onto ${\psi }_j$ instead givesAt second order, projecting the eigenvalue equation onto ${\psi }_0$ gives $E^{(2)}=⟨{\psi }_0,H^{\prime }\chi ⟩$. Expand $\chi$ in the orthonormal energy basis and use self-adjointness of $H^{\prime }$:Nondegeneracy ensures the denominators for this level do not vanish; convergence and validity of the expansion are among the assumed perturbation-theory hypotheses.

For the cosine perturbation of the ground level in a one-dimensional box, write $u=\pi x/a$. The product-to-sum identity givesso, with the given common normalization of the sine eigenfunctions,The diagonal matrix element is $-ϵ/2$, and the only nonzero off-diagonal matrix element out of the ground state is $⟨{\varphi }_3,V{\varphi }_1⟩=ϵ/2$. Let $E_{\mathrm{box}}={\pi }^2{\hslash }^2/(2m{a}^2)$. Since ${\mathcal{E}}_3=9E_{\mathrm{box}}$, the ground energy isThe second-order term is negative, as expected for a nondegenerate ground level: every excited-quantum state denominator is negative. The first-order shift is also negative for positive $ϵ$, because the ground-quantum state density is largest near the center, where this perturbing potential is negative.

From $H=a_{+}{a}_{-}/(2m)+\hslash \omega /2$ and the commutator product rule,Consequently, if $H\psi =E\psi$,Thus the creation operator raises the energy eigenvalue by $\hslash \omega$, and the annihilation operator lowers it by $\hslash \omega$, provided the resulting vector is nonzero. The zero vector is not an eigenstate; in particular the ground state will be annihilated by $a_{-}$. The displayed operator identity holds even in that case.