601. A metal is illuminated separately by photons of frequencies \(f\) and \(3f\). Both frequencies exceed its photoelectric threshold. The maximum kinetic energy of photoelectrons produced at \(3f\) is exactly five times that produced at \(f\).
The metal is then illuminated at frequency \(2f\). Assume the work function remains unchanged.
Which option correctly gives the threshold frequency and the ratio of maximum kinetic energies at \(2f\) and \(f\)?
ⓐ. Threshold \(f/3\); kinetic-energy ratio \(2\).
ⓑ. Threshold \(f/2\); kinetic-energy ratio \(3\).
ⓒ. Threshold \(2f/3\); kinetic-energy ratio \(4\).
ⓓ. Threshold \(f/2\); kinetic-energy ratio \(2\).
Correct Answer: Threshold \(f/2\); kinetic-energy ratio \(3\).
Explanation: \(\textbf{Express the first photoelectron kinetic energy:}\)
Einstein's photoelectric equation gives
\[
K_{\max}=hf-\phi
\]
For incident frequency \(f\),
\[
K_1=hf-\phi
\]
For incident frequency \(3f\),
\[
K_3=3hf-\phi
\]
\(\textbf{Use the measured kinetic-energy ratio:}\)
The problem states
\[
K_3=5K_1
\]
Substituting,
\[
3hf-\phi=5(hf-\phi)
\]
Expanding,
\[
3hf-\phi=5hf-5\phi
\]
Rearranging,
\[
4\phi=2hf
\]
\[
\phi=\frac{hf}{2}
\]
\(\textbf{Recover the threshold frequency:}\)
The work function is related to the threshold frequency by
\[
\phi=hf_0
\]
Therefore,
\[
hf_0=\frac{hf}{2}
\]
\[
f_0=\frac f2
\]
This is consistent with the stipulated fact that both original frequencies exceed threshold.
\(\textbf{Calculate the original maximum kinetic energy:}\)
\[
K_1=hf-\frac{hf}{2}
\]
\[
K_1=\frac{hf}{2}
\]
\(\textbf{Apply the new frequency }2f\textbf{:}\)
\[
K_2=h(2f)-\phi
\]
Substituting the inferred work function,
\[
K_2=2hf-\frac{hf}{2}
\]
\[
K_2=\frac{3hf}{2}
\]
\(\textbf{Compare the two kinetic energies:}\)
\[
\frac{K_2}{K_1}
=\frac{3hf/2}{hf/2}
\]
\[
\frac{K_2}{K_1}=3
\]
\(\textbf{Check against the original measurement:}\)
At frequency \(3f\),
\[
K_3=3hf-\frac{hf}{2}=\frac{5hf}{2}
\]
This gives
\[
\frac{K_3}{K_1}=5
\]
as observed.
\(\textbf{Interpret the non-proportional kinetic-energy changes:}\)
Photoelectron kinetic energy is linear in frequency but does not pass through the origin because the work function must first be supplied.
Tripling incident frequency therefore need not triple maximum electron kinetic energy.
The measured ratio instead reveals the work function relative to \(hf\).
That information allows the response at an intermediate frequency to be predicted.
\(\textbf{Final answer:}\)
\[
\boxed{f_0=\frac f2,\qquad\frac{K_2}{K_1}=3}
\]
602. Three monochromatic radiations P, Q and R travel in vacuum. Their measured quantities are:
| Radiation | Measured quantity | Value |
| P | Wavelength | \(300\,\mathrm{nm}\) |
| Q | Frequency | \(1.50\times10^{15}\,\mathrm{s^{-1}}\) |
| R | Wavenumber | \(4.00\times10^6\,\mathrm{m^{-1}}\) |
Use \(c=3.00\times10^8\,\mathrm{m\,s^{-1}}\). Suppose three beams deliver equal energy per second to identical detectors. Which option correctly orders the photon arrival rates and the photon energies?
ⓐ. Photon energies: \(P\gt Q\gt R\); arrival rates: \(R\gt Q\gt P\).
ⓑ. Photon energies: \(P\gt R\gt Q\); arrival rates: \(Q\gt R\gt P\).
ⓒ. Photon energies: \(Q\gt R\gt P\); arrival rates: \(Q\gt R\gt P\).
ⓓ. Photon energies: \(Q\gt R\gt P\); arrival rates: \(P\gt R\gt Q\).
Correct Answer: Photon energies: \(Q\gt R\gt P\); arrival rates: \(P\gt R\gt Q\).
Explanation: \(\textbf{Convert all observations to a common wavelength scale:}\)
For radiation P,
\[
\lambda_P=300\,\mathrm{nm}
\]
For Q, the vacuum wave relation is
\[
c=f_Q\lambda_Q
\]
Therefore,
\[
\lambda_Q=\frac{c}{f_Q}
\]
\[
\lambda_Q=\frac{3.00\times10^8}{1.50\times10^{15}}\,\mathrm m
\]
\[
\lambda_Q=2.00\times10^{-7}\,\mathrm m
\]
\[
\lambda_Q=200\,\mathrm{nm}
\]
For R, wavenumber is reciprocal wavelength:
\[
\tilde{\nu}_R=\frac1{\lambda_R}
\]
Thus,
\[
\lambda_R=\frac1{4.00\times10^6}\,\mathrm m
\]
\[
\lambda_R=2.50\times10^{-7}\,\mathrm m
\]
\[
\lambda_R=250\,\mathrm{nm}
\]
\(\textbf{Rank the energy of one photon:}\)
Photon energy varies inversely with vacuum wavelength:
\[
E_\gamma=\frac{hc}{\lambda}
\]
The wavelengths satisfy
\[
\lambda_Q\lt \lambda_R\lt \lambda_P
\]
Consequently,
\[
E_Q\gt E_R\gt E_P
\]
\(\textbf{Apply the equal-power condition:}\)
Optical power is photon energy delivered per unit time:
\[
\mathcal P=\dot N E_\gamma
\]
The three incident powers are equal.
Therefore,
\[
\dot N=\frac{\mathcal P}{E_\gamma}
\]
The photon arrival rate is inversely proportional to the energy of one photon.
Thus,
\[
\dot N_P\gt \dot N_R\gt \dot N_Q
\]
\(\textbf{Interpret the two opposite rankings:}\)
The highest-frequency radiation has the greatest energy per photon.
However, fewer of those higher-energy photons are needed to deliver a specified amount of energy per second.
Therefore, equal-power beams need not supply equal photon numbers.
Frequency and wavenumber must be converted into the same physical wavelength scale before making either comparison.
It also distinguishes frequency from wavenumber: they have different units even though both increase when wavelength decreases.
The two rankings are opposite because photon energy and photon arrival rate respond inversely under the equal-power condition.
603. Two electron beams, P and Q, have identical central de Broglie wavelengths and hence equal central momentum magnitudes. In P, the uncertainty in one position component is \(\Delta x_P=d\); in Q, it is \(\Delta x_Q=2d\).
Both beams are initially prepared at the minimum allowed momentum-component uncertainty according to Heisenberg's relation. A device then increases the central momentum magnitude of beam Q to twice its previous value without changing Q's actual absolute momentum uncertainty or position uncertainty.
Which option correctly compares the minimum initial absolute momentum uncertainties and the final fractional momentum uncertainty of Q relative to P's original fractional uncertainty?
ⓐ. Initially \(\Delta p_{x,Q}=\Delta p_{x,P}/2\); finally Q's fractional momentum uncertainty is one-fourth P's original fractional uncertainty.
ⓑ. Initially \(\Delta p_{x,Q}=2\Delta p_{x,P}\); finally Q's fractional momentum uncertainty equals P's original fractional uncertainty.
ⓒ. Initially their absolute uncertainties are equal; finally Q's fractional momentum uncertainty is half P's original fractional uncertainty.
ⓓ. Initially \(\Delta p_{x,Q}=\Delta p_{x,P}/2\); finally Q's fractional momentum uncertainty is twice P's original fractional uncertainty.
Correct Answer: Initially \(\Delta p_{x,Q}=\Delta p_{x,P}/2\); finally Q's fractional momentum uncertainty is one-fourth P's original fractional uncertainty.
Explanation: \(\textbf{Apply the original minimum-uncertainty preparations:}\)
Heisenberg's inequality is
\[
\Delta x\,\Delta p_x\geq\frac{\hbar}{2}
\]
At the stipulated minimum,
\[
\Delta p_x=\frac{\hbar}{2\Delta x}
\]
For beam P,
\[
\Delta p_{x,P}=\frac{\hbar}{2d}
\]
For beam Q,
\[
\Delta p_{x,Q}=\frac{\hbar}{2(2d)}
\]
\[
\Delta p_{x,Q}=\frac{\hbar}{4d}
\]
Thus,
\[
\frac{\Delta p_{x,Q}}{\Delta p_{x,P}}=\frac12
\]
\(\textbf{Compare initial fractional uncertainties:}\)
Let the common initial central momentum magnitude be \(p\).
For P,
\[
f_P=\frac{\Delta p_{x,P}}p=\frac{\hbar}{2dp}
\]
For Q,
\[
f_{Q,i}=\frac{\hbar}{4dp}
\]
Therefore,
\[
f_{Q,i}=\frac{f_P}{2}
\]
\(\textbf{Apply the changed central momentum:}\)
The device doubles Q's central momentum:
\[
p_{Q,f}=2p
\]
The problem explicitly states that Q's absolute uncertainty remains
\[
\Delta p_{x,Q,f}=\frac{\hbar}{4d}
\]
Its final fractional uncertainty is consequently
\[
f_{Q,f}=\frac{\Delta p_{x,Q,f}}{p_{Q,f}}
\]
\[
f_{Q,f}=\frac{\hbar/(4d)}{2p}
\]
\[
f_{Q,f}=\frac{\hbar}{8dp}
\]
\(\textbf{Compare with the original fraction for P:}\)
\[
\frac{f_{Q,f}}{f_P}
=\frac{\hbar/(8dp)}{\hbar/(2dp)}
\]
\[
\frac{f_{Q,f}}{f_P}=\frac14
\]
\(\textbf{Interpret the two independent changes:}\)
Q initially has a larger position uncertainty and therefore a smaller minimum absolute momentum uncertainty.
The later device changes Q's central momentum but not the width of its momentum distribution.
Consequently, the fractional momentum uncertainty decreases although the absolute uncertainty remains fixed.
The uncertainty principle constrains the product of the spreads, not the numerical value of the mean momentum.
Doubling a beam's central momentum does not automatically require doubling its momentum uncertainty.
This distinguishes a change in the average or central motion from a change in the precision of the quantum state.
\(\textbf{Final answer:}\)
\[
\boxed{\frac{\Delta p_{x,Q}}{\Delta p_{x,P}}=\frac12,\qquad\frac{f_{Q,f}}{f_P}=\frac14}
\]
604. The normalised hydrogen \(1s\) and \(2s\) orbitals have the following radial wave functions, where \(a_0\) is the Bohr radius:
\[
\Psi_{1s}(r)=\frac{1}{\sqrt{\pi a_0^3}}e^{-r/a_0}
\]
\[
\Psi_{2s}(r)=\frac{1}{4\sqrt{2\pi a_0^3}}\left(2-\frac r{a_0}\right)e^{-r/(2a_0)}
\]
At the nucleus and at \(r=4a_0\), the corresponding local probability densities are compared. Use \(e^4\approx54.6\).
Which option correctly gives the density ratios \(\rho_{2s}/\rho_{1s}\) at these two positions and explains the reversal in their relative magnitudes?
ⓐ. At the nucleus \(1/8\), and at \(4a_0\) approximately \(6.83\); the \(2s\) density is smaller at the nucleus but greater at the specified outer radius.
ⓑ. At the nucleus \(1/4\), and at \(4a_0\) approximately \(3.41\); the reversal occurs because probability density can become negative.
ⓒ. At the nucleus \(8\), and at \(4a_0\) approximately \(0.147\); the \(1s\) density dominates only at large radius.
ⓓ. At both positions \(1/8\); two orbitals with spherical symmetry must have the same radial dependence apart from normalisation.
Correct Answer: At the nucleus \(1/8\), and at \(4a_0\) approximately \(6.83\); the \(2s\) density is smaller at the nucleus but greater at the specified outer radius.
Explanation: \(\textbf{Square the two supplied wave functions:}\)
The local spatial probability density is the squared magnitude of the wave function.
For \(1s\),
\[
\rho_{1s}(r)=\frac1{\pi a_0^3}e^{-2r/a_0}
\]
For \(2s\),
\[
\rho_{2s}(r)=\frac1{32\pi a_0^3}
\left(2-\frac r{a_0}\right)^2e^{-r/a_0}
\]
\(\textbf{Form a common-radius density ratio:}\)
Dividing the two expressions,
\[
\frac{\rho_{2s}(r)}{\rho_{1s}(r)}
=\frac1{32}\left(2-\frac r{a_0}\right)^2e^{r/a_0}
\]
This relation includes both the polynomial nodal factor and the different exponential radial dependences.
\(\textbf{Evaluate the ratio at the nucleus:}\)
At \(r=0\),
\[
\left(\frac{\rho_{2s}}{\rho_{1s}}\right)_0
=\frac1{32}(2)^2e^0
\]
\[
\left(\frac{\rho_{2s}}{\rho_{1s}}\right)_0
=\frac4{32}
\]
\[
\left(\frac{\rho_{2s}}{\rho_{1s}}\right)_0=\frac18
\]
Therefore, the \(1s\) local density is eight times the \(2s\) local density at the nucleus.
\(\textbf{Evaluate the ratio at }r=4a_0\textbf{:}\)
Substituting \(r/a_0=4\),
\[
\left(\frac{\rho_{2s}}{\rho_{1s}}\right)_{4a_0}
=\frac1{32}(2-4)^2e^4
\]
\[
\left(\frac{\rho_{2s}}{\rho_{1s}}\right)_{4a_0}
=\frac{e^4}{8}
\]
Using the supplied exponential value,
\[
\left(\frac{\rho_{2s}}{\rho_{1s}}\right)_{4a_0}
\approx\frac{54.6}{8}
\]
\[
\left(\frac{\rho_{2s}}{\rho_{1s}}\right)_{4a_0}\approx6.83
\]
\(\textbf{Check the radial-node condition:}\)
The \(2s\) wave function vanishes where
\[
2-\frac r{a_0}=0
\]
Thus, its radial node occurs at
\[
r=2a_0
\]
At this radius the \(2s\) density is zero, but the \(1s\) density is positive.
\(\textbf{Interpret the spatial-density reversal:}\)
The \(1s\) density is more concentrated near the nucleus.
The \(2s\) wave function has a radial node and a more extended outer region.
Its probability density can consequently exceed the \(1s\) density at a sufficiently large radius.
Neither density is negative, even though the real \(2s\) wave function changes sign across its node.
The local-density comparison also does not directly give the total probability outside a spherical boundary, which requires integration over volume.
\(\textbf{Final answer:}\)
\[
\boxed{\left(\frac{\rho_{2s}}{\rho_{1s}}\right)_0=\frac18,\qquad
\left(\frac{\rho_{2s}}{\rho_{1s}}\right)_{4a_0}\approx6.83}
\]
605. A normalised real atomic orbital has wave function \(\Psi(\mathbf r)\), satisfying
\[
\int_{\mathrm{all\ space}}|\Psi|^2\,dV=1
\]
Three proposed descriptions of the same spatial state are considered:
P: \(-\Psi\);
Q: \(2\Psi\);
R: \(\tfrac12\Psi\).
An investigator claims that all three expressions already represent normalised versions of the same state because multiplying an orbital by a constant cannot affect probability.
Which option correctly evaluates this claim?
ⓐ. P, Q and R are all normalised and have equal probability densities because only the shape of a wave function matters.
ⓑ. P stays normalised with unchanged density; Q and R have the same spatial shape but require renormalisation.
ⓒ. Q is normalised because its wave-function magnitude is greater; P and R cannot represent allowed atomic states.
ⓓ. P changes every electron probability from positive to negative; Q doubles total probability and R halves it.
Correct Answer: P stays normalised with unchanged density; Q and R have the same spatial shape but require renormalisation.
Explanation: The normalisation condition assigns total spatial probability one to an orbital state.
For the original wave function,
\[
\int|\Psi|^2\,dV=1
\]
Multiplication of a wave function by a constant changes the integral of its squared magnitude unless the constant has magnitude one.
For P, the transformed wave function is \(-\Psi\).
Its squared magnitude is
\[
|-\Psi|^2=|\Psi|^2
\]
Therefore, P remains normalised and gives exactly the same spatial probability density.
The overall sign change is not an observable change in electron-position probability.
For Q, the transformed wave function is \(2\Psi\).
Its squared magnitude is four times that of the original wave function.
Consequently, its integral over all space is four rather than one.
It is therefore not normalised as written.
For R, the transformed wave function is \(\Psi/2\).
Its squared magnitude is one-fourth of the original density.
Its probability integral is consequently one-fourth rather than one.
Neither Q nor R can be used directly as a normalised orbital wave function in its stated form.
However, both retain the original wave function's spatial dependence and nodal locations up to an overall nonzero scale.
After renormalisation, they describe the same spatial probability distribution as \(\Psi\).
The investigator is correct that multiplication by a nonzero constant need not change the physical spatial state, but incorrect that every such rescaled expression is already normalised.
The distinction is between an unchanged state after appropriate normalisation and an unchanged numerical probability density before normalisation.
606. Two real atomic orbitals have the following spatial forms, with positive radial functions \(f(r)\) and \(g(r)\):
\[
\Psi_P(x,y,z)=xf(r),\qquad
\Psi_Q(x,y,z)=xyg(r)
\]
Consider two opposite points A and B related by inversion through the nucleus:
\[
A=(a,b,c),\qquad B=(-a,-b,-c)
\]
where \(a\neq0\), \(b\neq0\), and both radial factors are nonzero at the common radius.
Which option correctly compares wave-function signs and local probability densities at A and B?
ⓐ. Both P and Q reverse wave-function sign under inversion, but both retain equal densities at the two points.
ⓑ. P reverses wave-function sign, Q retains its sign, and each orbital has equal local probability densities at A and B.
ⓒ. P retains its wave-function sign, Q reverses its sign, and both acquire negative probability density at B.
ⓓ. P and Q both retain their signs, but their densities change because inversion changes the radial distance from the nucleus.
Correct Answer: P reverses wave-function sign, Q retains its sign, and each orbital has equal local probability densities at A and B.
Explanation: The two selected positions have opposite Cartesian coordinates.
However, their distances from the nucleus are equal:
\[
r_A=\sqrt{a^2+b^2+c^2}
\]
\[
r_B=\sqrt{(-a)^2+(-b)^2+(-c)^2}=r_A
\]
Therefore, the radial factors have the same values at both positions.
For P, the wave function is proportional to the \(x\) coordinate.
At A,
\[
\Psi_P(A)=af(r_A)
\]
At B,
\[
\Psi_P(B)=-af(r_A)
\]
Thus, P changes sign under inversion.
Its squared magnitude does not change:
\[
|\Psi_P(B)|^2=|\Psi_P(A)|^2
\]
For Q, the angular factor is the product \(xy\).
At A,
\[
\Psi_Q(A)=abg(r_A)
\]
At B,
\[
\Psi_Q(B)=(-a)(-b)g(r_A)
\]
\[
\Psi_Q(B)=abg(r_A)
\]
Therefore, Q retains its sign under inversion.
Its probability density is also unchanged.
The different sign behaviours arise from the different angular factors of the two orbitals.
The \(x\) factor changes sign once, whereas the \(xy\) product contains two coordinate sign changes that cancel.
Neither reversal nor preservation of the wave-function sign requires unequal electron-position probabilities at the opposite points.
The comparison distinguishes the mathematical phase behaviour of orbital wave functions from their observable spatial probability densities.
It also illustrates why different orbital shapes can be characterised through directional relationships without treating wave-function sign as a negative probability.
607. Two hydrogen atoms are independently prepared, one in a \(2s\) orbital and the other in a \(2p_z\) orbital. The \(2s\) orbital has its finite radial node at radius \(r_0\). At a point A on the positive \(z\)-axis, with radial distance \(r_0\), the \(2p_z\) wave function is nonzero.
Both atoms are exposed separately to photons of energy \(4.00\,\mathrm{eV}\). Assume the elementary hydrogen energy formula \(E_n=-13.6/n^2\,\mathrm{eV}\), a one-photon process and negligible recoil.
Which option correctly connects the spatial measurements with the ionisation outcomes?
ⓐ. The \(2s\) atom cannot be ionised because the wave function is zero at A, whereas the \(2p_z\) atom produces a \(0.60\,\mathrm{eV}\) photoelectron.
ⓑ. The two orbitals have different ionisation energies because their nodal structures differ, so the photon can ionise only \(2p_z\).
ⓒ. Both ionise with \(0.60\,\mathrm{eV}\) photoelectrons; differing local densities at A do not alter equal \(n=2\) binding energies.
ⓓ. Both atoms can be ionised, but the \(2s\) photoelectron has greater kinetic energy because an \(s\) orbital has no angular node.
Correct Answer: Both ionise with \(0.60\,\mathrm{eV}\) photoelectrons; differing local densities at A do not alter equal \(n=2\) binding energies.
Explanation: \(\textbf{Interpret the pointwise spatial evidence:}\)
The \(2s\) orbital possesses one finite spherical radial node at \(r=r_0\).
Its wave function and local probability density therefore vanish at every point on that nodal sphere.
In particular,
\[
\rho_{2s}(A)=0
\]
The \(2p_z\) orbital has a different nodal geometry.
At A, its wave function is explicitly stated to be nonzero.
Hence,
\[
\rho_{2p_z}(A)\gt 0
\]
The orbitals consequently have different spatial probability distributions.
\(\textbf{Determine their energies in the elementary hydrogen model:}\)
For a hydrogen atom,
\[
E_n=-\frac{13.6}{n^2}\,\mathrm{eV}
\]
Both orbitals have principal quantum number two.
Therefore,
\[
E_{2s}=E_{2p}=-\frac{13.6}{4}
\]
\[
E_{2s}=E_{2p}=-3.40\,\mathrm{eV}
\]
This equality is the gross-energy degeneracy of the elementary one-electron Coulombic treatment.
\(\textbf{Find the common ionisation threshold:}\)
The continuum reference energy is zero.
Hence, the ionisation energy from either orbital is
\[
E_{\mathrm{ion}}=0-(-3.40)
\]
\[
E_{\mathrm{ion}}=3.40\,\mathrm{eV}
\]
\(\textbf{Apply the incident photon energy:}\)
Each incident photon carries
\[
E_\gamma=4.00\,\mathrm{eV}
\]
This exceeds the common threshold.
The electron kinetic energy is
\[
K=E_\gamma-E_{\mathrm{ion}}
\]
\[
K=4.00-3.40
\]
\[
K=0.60\,\mathrm{eV}
\]
\(\textbf{Interpret the independence of spatial shape and binding energy:}\)
A zero of probability density at one spatial point does not prevent the electron from occupying the complete orbital or being ionised.
The nodal geometry describes the wave function's spatial structure.
The ionisation threshold instead depends on the total electronic energy of the initial state.
In the elementary hydrogen model, states with the same principal quantum number can have different nodal structures while retaining equal energies.
Consequently, the two photoelectrons can have equal kinetic energies despite the different position probabilities measured at A.
\(\textbf{Final answer:}\)
\[
E_{\mathrm{ion},2s}=E_{\mathrm{ion},2p}=3.40\,\mathrm{eV},\qquad K_{2s}=K_{2p}=0.60\,\mathrm{eV}
\]
608. A student prepares three possible descriptions of a hydrogen atom initially in a \(1s\) state.
Description P: The atom has a well-defined electronic energy, but its electron is described by a spatial probability distribution rather than an exactly known circular trajectory.
Description Q: The atom has a well-defined electronic energy, and therefore the electron's position and momentum can both be specified without uncertainty.
Description R: The probability density is nonzero at the nucleus, so the electron must remain permanently at the nucleus rather than being found at other positions.
The student is then told that incident radiation can excite the atom only through a permitted energy difference.
Which conclusion correctly combines the quantum mechanical orbital interpretation with the energy-selective absorption condition?
ⓐ. P is compatible with discrete energies and probabilistic positions; photon absorption still needs an allowed energy gap.
ⓑ. Q is compatible because definite electronic energy removes Heisenberg's position-momentum restriction; arbitrary photon energies can then be absorbed.
ⓒ. R is compatible because maximum density at the nucleus means every excitation begins from an electron fixed at zero radius.
ⓓ. P and R are both compatible, but Q is not, because the density at the nucleus determines the energy of every photon the atom can absorb.
Correct Answer: P is compatible with discrete energies and probabilistic positions; photon absorption still needs an allowed energy gap.
Explanation: A stationary atomic state can possess a characteristic electronic energy without assigning a definite classical trajectory to its electron.
This is a central feature of the quantum mechanical description.
The spatial orbital is represented mathematically by a wave function.
Its squared magnitude gives the electron's spatial probability density.
Therefore, Description P correctly combines a characteristic electronic energy with a probabilistic account of electron position.
Description Q is incorrect because definite electronic energy does not remove the position-momentum uncertainty principle.
A stationary state is not equivalent to an electron travelling around a precisely defined circular path with exactly known position and momentum.
The uncertainty relation continues to constrain the simultaneous precision of corresponding position and momentum components.
Description R is also incorrect.
A nonzero or even maximum local probability density at the nucleus does not mean that the electron is permanently located there.
The \(1s\) electron has a spatial probability distribution extending over a finite region around the nucleus and beyond any customary boundary surface.
An electron-position measurement may yield different positions in repeated preparations.
The permitted electronic energies determine the energy changes possible between bound states.
For an ideal one-photon bound-bound absorption process, the photon energy must correspond to an allowed electronic energy difference.
This requirement is independent of assigning the electron a classical trajectory.
Thus, the probabilistic orbital description and energy quantisation are complementary features of quantum mechanics.
A spatial density maximum does not itself set the absorbed photon energy; the difference between the initial and final electronic energies does.
Description P is the only one consistent with both the spatial and spectroscopic aspects of the model.
609. The radial wave function of a hydrogen \(1s\) orbital is represented by
\[
\Psi(r)=Ae^{-r/a}
\]
where \(A\gt 0\) and \(a\gt 0\). Two very thin concentric spherical shells of equal thickness are centred at radii \(r_1=a\ln2\) and \(r_2=2a\ln2\).
Assume the shell thickness is sufficiently small that the probability in each shell is proportional to \(r^2|\Psi(r)|^2\Delta r\).
Which option correctly compares the wave-function amplitudes, local probability densities and shell probabilities at these radii?
ⓐ. \(\Psi(r_2)/\Psi(r_1)=1/2\); \(\rho(r_2)/\rho(r_1)=1/4\); \(P_2/P_1=1\).
ⓑ. \(\Psi(r_2)/\Psi(r_1)=1/2\); \(\rho(r_2)/\rho(r_1)=1/2\); \(P_2/P_1=2\).
ⓒ. \(\Psi(r_2)/\Psi(r_1)=1/4\); \(\rho(r_2)/\rho(r_1)=1/16\); \(P_2/P_1=1/4\).
ⓓ. \(\Psi(r_2)/\Psi(r_1)=1/2\); \(\rho(r_2)/\rho(r_1)=1/4\); \(P_2/P_1=1/4\).
Correct Answer: \(\Psi(r_2)/\Psi(r_1)=1/2\); \(\rho(r_2)/\rho(r_1)=1/4\); \(P_2/P_1=1\).
Explanation: \(\textbf{Compare the radial wave-function amplitudes:}\)
The supplied expression is
\[
\Psi(r)=Ae^{-r/a}
\]
At the first radius,
\[
\Psi(r_1)=Ae^{-\ln2}
\]
\[
\Psi(r_1)=\frac A2
\]
At the second radius,
\[
\Psi(r_2)=Ae^{-2\ln2}
\]
\[
\Psi(r_2)=\frac A4
\]
Therefore,
\[
\frac{\Psi(r_2)}{\Psi(r_1)}=\frac{A/4}{A/2}
\]
\[
\frac{\Psi(r_2)}{\Psi(r_1)}=\frac12
\]
\(\textbf{Convert amplitudes to local probability densities:}\)
The local spatial probability density is
\[
\rho(r)=|\Psi(r)|^2
\]
For the two radii,
\[
\rho(r_1)=\frac{A^2}{4}
\]
\[
\rho(r_2)=\frac{A^2}{16}
\]
Thus,
\[
\frac{\rho(r_2)}{\rho(r_1)}=\frac14
\]
\(\textbf{Include the geometry of the spherical shells:}\)
The probability associated with a thin complete spherical shell is
\[
\Delta P\approx4\pi r^2\rho(r)\Delta r
\]
The shells have equal thickness, so
\[
\frac{P_2}{P_1}=\frac{r_2^2}{r_1^2}\frac{\rho(r_2)}{\rho(r_1)}
\]
Since \(r_2=2r_1\),
\[
\frac{P_2}{P_1}=2^2\left(\frac14\right)
\]
\[
\frac{P_2}{P_1}=1
\]
\(\textbf{Interpret the three comparisons:}\)
The wave-function amplitude decreases by a factor of two.
Its squared magnitude consequently decreases by a factor of four.
However, the second spherical shell has four times the geometrical area of the first.
For equal small thicknesses, the area increase exactly compensates for the local-density decrease.
Therefore, the two shells have equal approximate probabilities despite different wave-function amplitudes and local densities.
The result illustrates why a graph of \(\Psi^2\) against radial distance must not be interpreted directly as the probability in equal-thickness spherical shells.
\(\textbf{Final answer:}\)
\[
\boxed{\frac{\Psi(r_2)}{\Psi(r_1)}=\frac12,\qquad\frac{\rho(r_2)}{\rho(r_1)}=\frac14,\qquad\frac{P_2}{P_1}=1}
\]
610. A boundary-surface representation of a spherically symmetric \(1s\) orbital is constructed so that a sphere of radius \(R\) contains exactly \(90\%\) of the total electron-position probability.
The sphere is divided into eight equal octants by three mutually perpendicular coordinate planes through the nucleus. The probability outside the sphere is also examined separately in the positive-\(z\) half-space.
Assume the orbital's probability distribution is spherically symmetric throughout space.
Which option correctly gives the probabilities in one selected octant inside the sphere, outside the sphere in the positive-\(z\) half-space, and in the entire positive-\(z\) half-space?
ⓐ. \(12.5\%,\ 10\%,\ 50\%\)
ⓑ. \(11.25\%,\ 5\%,\ 50\%\)
ⓒ. \(11.25\%,\ 10\%,\ 55\%\)
ⓓ. \(45\%,\ 5\%,\ 90\%\)
Correct Answer: \(11.25\%,\ 5\%,\ 50\%\)
Explanation: \(\textbf{Interpret the orbital boundary:}\)
The stipulated spherical boundary encloses \(90\%\) of the total electron-position probability.
Therefore,
\[
P_{\mathrm{inside}}=0.90
\]
The probability outside is
\[
P_{\mathrm{outside}}=1-0.90
\]
\[
P_{\mathrm{outside}}=0.10
\]
The boundary is a chosen probability surface, not a wall beyond which the electron cannot be detected.
\(\textbf{Distribute the enclosed probability among octants:}\)
A spherically symmetric orbital has no preferred spatial direction.
The eight octants defined by the coordinate planes consequently contain equal portions of the probability enclosed by the sphere.
Thus,
\[
P_{\mathrm{one\ octant}}=\frac{0.90}{8}
\]
\[
P_{\mathrm{one\ octant}}=0.1125
\]
\[
P_{\mathrm{one\ octant}}=11.25\%
\]
\(\textbf{Examine the probability beyond the selected boundary:}\)
The total probability outside the sphere is \(10\%\).
Spherical symmetry divides this probability equally between the positive-\(z\) and negative-\(z\) half-spaces.
Therefore,
\[
P_{\mathrm{outside},z\gt 0}=\frac{0.10}{2}
\]
\[
P_{\mathrm{outside},z\gt 0}=0.05
\]
\[
P_{\mathrm{outside},z\gt 0}=5\%
\]
\(\textbf{Calculate the probability in the complete upper half-space:}\)
Half of the \(90\%\) enclosed probability lies above the \(xy\)-plane.
Hence,
\[
P_{\mathrm{inside},z\gt 0}=\frac{0.90}{2}
\]
\[
P_{\mathrm{inside},z\gt 0}=0.45
\]
Adding the probability outside the spherical boundary,
\[
P_{z\gt 0}=0.45+0.05
\]
\[
P_{z\gt 0}=0.50
\]
\(\textbf{Interpret the distinct sampling regions:}\)
An octant inside the boundary is not one-eighth of all space in the probability-accounting sense used here; it is one-eighth of the enclosed probability.
The positive-\(z\) half-space, by contrast, extends both inside and outside the selected sphere.
The complete upper half-space therefore contains \(50\%\) of the total probability.
These results follow from spherical symmetry and the boundary's specified enclosed probability.
They do not require the detailed radial formula of the \(1s\) wave function.
\(\textbf{Final answer:}\)
\[
\boxed{P_{\mathrm{octant}}=11.25\%,\qquad P_{\mathrm{outside},z\gt 0}=5\%,\qquad P_{z\gt 0}=50\%}
\]
611. A hydrogen \(2s\) orbital has one finite radial node at radius \(r_0\). An investigator plots the cumulative radial probability
\[
F(r)=\text{Probability that the electron is found at a distance not exceeding }r
\]
against \(r\). The plot indicates \(F(r_0)=0.30\).
A proposed interpretation says that because the local probability density is zero at \(r_0\), the cumulative probability must remain exactly \(0.30\) throughout a finite interval immediately beyond the node.
Which option correctly evaluates this claim?
ⓐ. It is correct because a radial node divides the orbital into two permanently isolated probability regions.
ⓑ. It is correct provided the real wave function is negative beyond \(r_0\), so added probability cancels previously accumulated probability.
ⓒ. It is incorrect because cumulative probability must decrease immediately after a radial node as the wave function changes sign.
ⓓ. It is incorrect; the nodal sphere has zero density only at one radius, and \(F(r)\) can increase beyond it.
Correct Answer: It is incorrect; the nodal sphere has zero density only at one radius, and \(F(r)\) can increase beyond it.
Explanation: The \(2s\) orbital has one finite radial node at \(r=r_0\).
At the node, its real wave function vanishes.
The local spatial probability density is therefore zero on the corresponding spherical surface.
The radial probability distribution \(4\pi r^2|\Psi(r)|^2\) is also zero at that radius.
However, these statements concern one radial position rather than an entire finite interval.
A \(2s\) wave function becomes nonzero again outside its radial node.
Its sign may be opposite to the sign in the inner region, but its squared magnitude is positive wherever the wave function is nonzero.
The cumulative probability \(F(r)\) includes all probability enclosed within the sphere of radius \(r\).
As the sphere expands, previously included probability is not removed.
The probability added between two radii is obtained from the nonnegative radial distribution over that interval.
Therefore, \(F(r)\) cannot decrease with increasing radius.
A node can produce a zero radial probability density at one radius without producing a finite plateau in the cumulative probability curve.
Under the ordinary \(2s\) radial distribution, every finite radial interval beyond the node contains some nonzero probability.
Thus, for a radius sufficiently beyond the node,
\[
F(r)\gt F(r_0)=0.30
\]
while normalisation requires \(F(r)\) to approach one at large radial distance.
The investigator has confused a zero in the local wave-function amplitude with the absence of probability throughout a surrounding volume.
The distinction is essential when interpreting \(\Psi\), \(\Psi^2\), radial probability distributions and cumulative probability graphs for the same orbital.
612. The normalised ground-state \(1s\) wave function for a hydrogen-like one-electron species of nuclear charge \(Z\) is supplied as
\[
\Psi_Z(r)=\left(\frac{Z^3}{\pi a_0^3}\right)^{1/2}e^{-Zr/a_0}
\]
where \(a_0\) is the first Bohr radius of hydrogen. Compare hydrogen (\(Z=1\)) and \(\mathrm{He^+}\) (\(Z=2\)), neglecting reduced-mass corrections.
Use \(\ln8=2.079\). Which option correctly gives the ratio of their local probability densities at the nucleus, the radial distance where their local densities become equal, and their ground-state binding-energy ratio \(|E_{\mathrm{He^+}}|/|E_{\mathrm H}|\)?
ⓐ. \(4;\ 0.693a_0;\ 8\)
ⓑ. \(8;\ 2.079a_0;\ 4\)
ⓒ. \(8;\ 1.040a_0;\ 4\)
ⓓ. \(4;\ 1.040a_0;\ 2\)
Correct Answer: \(8;\ 1.040a_0;\ 4\)
Explanation: \(\textbf{Obtain the spatial probability density:}\)
Squaring the supplied wave function gives
\[
\rho_Z(r)=|\Psi_Z(r)|^2
\]
\[
\rho_Z(r)=\frac{Z^3}{\pi a_0^3}e^{-2Zr/a_0}
\]
\(\textbf{Compare the two species at the nucleus:}\)
At \(r=0\), the exponential factor equals one.
For hydrogen,
\[
\rho_{\mathrm H}(0)=\frac1{\pi a_0^3}
\]
For \(\mathrm{He^+}\),
\[
\rho_{\mathrm{He^+}}(0)=\frac8{\pi a_0^3}
\]
Therefore,
\[
\frac{\rho_{\mathrm{He^+}}(0)}{\rho_{\mathrm H}(0)}=8
\]
\(\textbf{Construct the density ratio at an arbitrary radius:}\)
At the same radial distance \(r\),
\[
\frac{\rho_{\mathrm{He^+}}(r)}{\rho_{\mathrm H}(r)}
=\frac{8e^{-4r/a_0}}{e^{-2r/a_0}}
\]
\[
\frac{\rho_{\mathrm{He^+}}(r)}{\rho_{\mathrm H}(r)}
=8e^{-2r/a_0}
\]
\(\textbf{Find the radius at which the densities become equal:}\)
Equality requires
\[
8e^{-2r/a_0}=1
\]
Therefore,
\[
e^{-2r/a_0}=\frac18
\]
Taking natural logarithms,
\[
-\frac{2r}{a_0}=-\ln8
\]
\[
r=\frac{a_0\ln8}{2}
\]
Substituting,
\[
r=\frac{2.079a_0}{2}
\]
\[
r\approx1.040a_0
\]
\(\textbf{Compare ground-state binding energies:}\)
For a hydrogen-like species,
\[
|E_n|=13.6\frac{Z^2}{n^2}\,\mathrm{eV}
\]
Both systems are in \(n=1\).
Therefore,
\[
\frac{|E_{\mathrm{He^+}}|}{|E_{\mathrm H}|}=\frac{2^2}{1^2}
\]
\[
\frac{|E_{\mathrm{He^+}}|}{|E_{\mathrm H}|}=4
\]
\(\textbf{Interpret the crossing of local densities:}\)
The larger nuclear charge produces a more concentrated ground-state electron distribution.
The \(\mathrm{He^+}\) density is eight times the hydrogen density at the nucleus.
However, the stronger radial exponential decay allows the hydrogen density to become greater beyond the calculated crossing radius.
The stronger binding of \(\mathrm{He^+}\) is consistent with its more compact spatial distribution.
Local density equality at one radius does not imply equality of the complete wave functions or their energies.
\(\textbf{Final answer:}\)
\[
\boxed{\frac{\rho_{\mathrm{He^+}}(0)}{\rho_{\mathrm H}(0)}=8,\qquad r_{\mathrm{equal}}\approx1.040a_0,\qquad\frac{|E_{\mathrm{He^+}}|}{|E_{\mathrm H}|}=4}
\]
613. A proposed atomic wave function is required to be normalisable so that its total electron-position probability can be made equal to one. Consider the following spherically symmetric trial functions over all space:
\[
\Psi_P(r)=Ae^{-r/a},\qquad
\Psi_Q(r)=A(1+e^{-r/a})
\]
where \(A\neq0\) and \(a\gt 0\).
An investigator argues that both functions can represent normalised bound-state orbitals because both have finite values at every finite radial distance.
Which assessment is correct?
ⓐ. Both functions can be normalised because their values remain finite at any selected point.
ⓑ. Neither function can be normalised because both are nonzero at the nucleus.
ⓒ. P is normalisable; Q is not, because its probability density approaches a nonzero constant at large distances.
ⓓ. Q can be normalised but P cannot, because a bound-state wave function must increase with radial distance.
Correct Answer: P is normalisable; Q is not, because its probability density approaches a nonzero constant at large distances.
Explanation: \(\textbf{Distinguish local finiteness from total normalisation:}\)
The probability density associated with a wave function is its squared magnitude.
For a normalised bound-state orbital, the integral of this density over all space must equal one.
A function being finite at each individual point does not establish that its density has a finite total integral.
The amount of spatial volume available at increasing radial distance must also be considered.
\(\textbf{Examine the large-distance behaviour of P:}\)
For P,
\[
\Psi_P(r)=Ae^{-r/a}
\]
As \(r\) becomes large,
\[
\Psi_P(r)\rightarrow0
\]
Its probability density decreases as
\[
|\Psi_P(r)|^2=A^2e^{-2r/a}
\]
The exponential decay is sufficiently rapid that the density can be integrated over all space to obtain a finite result.
An appropriate choice of the overall normalisation constant can therefore make its total probability one.
\(\textbf{Examine the large-distance behaviour of Q:}\)
For Q,
\[
\Psi_Q(r)=A(1+e^{-r/a})
\]
At large radial distance,
\[
\Psi_Q(r)\rightarrow A
\]
Therefore,
\[
|\Psi_Q(r)|^2\rightarrow A^2
\]
The density approaches a positive constant rather than zero.
\(\textbf{Apply the spherical-volume requirement:}\)
The volume of a thin spherical shell is approximately \(4\pi r^2dr\).
For Q at sufficiently large radius, its probability contribution behaves like
\[
dP\propto4\pi A^2r^2dr
\]
The available spherical-shell volume grows with radius.
Accumulating these contributions to arbitrarily large distances produces a divergent total rather than a finite probability integral.
Q cannot consequently be normalised over all space while \(A\neq0\).
\(\textbf{Interpret the conclusion:}\)
The proposed Q function is locally finite but fails the global probability requirement.
P passes this necessary normalisation test.
However, being normalisable is not, by itself, proof that a proposed function is an allowed stationary atomic orbital.
An actual stationary orbital must also satisfy the appropriate quantum mechanical equation and physical boundary conditions.
The investigator's error is to replace the total-probability requirement with the much weaker condition of finiteness at individual positions.
614. A real \(2p_z\) orbital is represented by a two-lobed boundary surface enclosing exactly \(90\%\) of the electron-position probability. The positive-\(z\) and negative-\(z\) lobes are mirror images under reflection through the \(xy\)-plane, which is an angular nodal plane.
The remaining probability lies outside the drawn boundary surface. Which option correctly describes the probability distribution and the significance of the wave-function signs in the two lobes?
ⓐ. Each lobe contains \(45\%\); their exterior regions together contain \(10\%\); opposite wave-function signs do not negate probabilities.
ⓑ. The positive-\(z\) lobe contains \(90\%\) probability and the negative-\(z\) lobe contains \(-90\%\), giving zero net probability.
ⓒ. Each drawn lobe contains \(50\%\) probability because the angular nodal plane prevents electron detection outside the drawn surface.
ⓓ. Each drawn lobe contains \(40\%\) probability; the missing \(20\%\) is concentrated entirely on the nodal plane.
Correct Answer: Each lobe contains \(45\%\); their exterior regions together contain \(10\%\); opposite wave-function signs do not negate probabilities.
Explanation: The boundary surface is stipulated to enclose \(90\%\) of the total electron-position probability.
It consists of two mirror-related lobes.
For a real \(2p_z\) orbital, the spatial probability density is symmetric under reflection through the \(xy\)-plane.
The probability associated with the part of the orbital on the positive-\(z\) side is consequently equal to that on the negative-\(z\) side.
The two drawn lobes therefore divide the enclosed \(90\%\) probability equally.
Each contains \(45\%\) of the total probability.
The probability outside the complete drawn boundary is \(10\%\).
The boundary is not an impenetrable wall; it is a chosen surface for representing a large fraction of the electron cloud.
The real \(p_z\) wave function conventionally has opposite signs in its two principal lobes.
However, the squared magnitude of the wave function gives the local probability density.
Squaring removes the sign of a real wave-function amplitude.
Both lobes consequently have nonnegative probability densities.
The intervening \(xy\)-plane is an angular nodal plane on which the wave function vanishes.
That zero-density plane is not a location where the unrepresented \(10\%\) probability is stored.
The two lobes also do not constitute two independent spatial orbitals.
Together they describe one \(2p_z\) spatial wave function.
The experiment therefore distinguishes the wave-function sign, the symmetry of probability density and the probabilistic meaning of an orbital boundary surface.
615. Two monochromatic beams pass through a transparent, non-absorbing glass plate of refractive index \(1.50\) and subsequently emerge into vacuum before striking the same photoelectric metal.
Their vacuum wavelengths before entering the plate are \(450\,\mathrm{nm}\) for P and \(350\,\mathrm{nm}\) for Q. The metal's threshold wavelength, stated for radiation in vacuum, is \(400\,\mathrm{nm}\).
Assume the frequency of each beam remains unchanged during refraction. Use \(hc=1240\,\mathrm{eV\,nm}\).
Which option correctly compares their wavelengths inside glass and predicts the photoelectric response?
ⓐ. Both wavelengths become smaller than \(400\,\mathrm{nm}\) inside glass, so both beams produce photoelectrons after leaving the plate.
ⓑ. P has wavelength \(300\,\mathrm{nm}\) and Q approximately \(233\,\mathrm{nm}\) inside glass; only Q causes photoemission, with \(K_{\max}\approx0.443\,\mathrm{eV}\).
ⓒ. P retains wavelength \(450\,\mathrm{nm}\) inside glass, while Q retains \(350\,\mathrm{nm}\); only Q emits photoelectrons with \(K_{\max}\approx3.54\,\mathrm{eV}\).
ⓓ. P has wavelength \(300\,\mathrm{nm}\) and Q approximately \(233\,\mathrm{nm}\) inside glass; both cause photoemission because their frequencies increase during refraction.
Correct Answer: P has wavelength \(300\,\mathrm{nm}\) and Q approximately \(233\,\mathrm{nm}\) inside glass; only Q causes photoemission, with \(K_{\max}\approx0.443\,\mathrm{eV}\).
Explanation: \(\textbf{Determine the wavelengths during passage through glass:}\)
The refractive index is
\[
n=\frac cv
\]
Therefore, the speed of light in glass is \(v=c/n\).
Frequency remains unchanged at the boundary, while wavelength changes according to
\[
\lambda_{\mathrm{glass}}=\frac{\lambda_{\mathrm{vac}}}{n}
\]
For P,
\[
\lambda_{P,\mathrm{glass}}=\frac{450}{1.50}
\]
\[
\lambda_{P,\mathrm{glass}}=300\,\mathrm{nm}
\]
For Q,
\[
\lambda_{Q,\mathrm{glass}}=\frac{350}{1.50}
\]
\[
\lambda_{Q,\mathrm{glass}}\approx233\,\mathrm{nm}
\]
\(\textbf{Identify the quantity governing the photoelectric threshold:}\)
Photon energy is determined by its frequency:
\[
E_\gamma=hf
\]
Refraction changes wavelength and propagation speed, but not the photon frequency.
Therefore, passage through the transparent glass does not change the photon energy.
The vacuum threshold wavelength must be compared with the beams' vacuum wavelengths or, equivalently, their unchanged frequencies.
\(\textbf{Calculate the metal's work function:}\)
\[
\phi=\frac{hc}{\lambda_0}
\]
\[
\phi=\frac{1240}{400}
\]
\[
\phi=3.10\,\mathrm{eV}
\]
\(\textbf{Test beam P:}\)
\[
E_P=\frac{1240}{450}
\]
\[
E_P\approx2.756\,\mathrm{eV}
\]
Since
\[
E_P\lt \phi
\]
beam P cannot cause photoemission.
Its wavelength becoming \(300\,\mathrm{nm}\) inside glass does not raise its photon energy above threshold.
\(\textbf{Test beam Q:}\)
\[
E_Q=\frac{1240}{350}
\]
\[
E_Q\approx3.543\,\mathrm{eV}
\]
Since \(E_Q\gt \phi\), photoemission is possible.
The maximum kinetic energy is
\[
K_{\max}=E_Q-\phi
\]
\[
K_{\max}=3.543-3.100
\]
\[
K_{\max}\approx0.443\,\mathrm{eV}
\]
\(\textbf{Interpret the changed propagation medium:}\)
A photon does not become more energetic merely because its wavelength is shorter in a medium of lower propagation speed.
The relation \(E=hc/\lambda\) uses the corresponding vacuum wavelength when \(c\) is the vacuum speed of light.
Inside glass, the appropriate wave relation is \(v=f\lambda_{\mathrm{glass}}\).
The photoelectric outcome depends on photon energy, not on comparing a wavelength measured inside glass directly with a threshold wavelength defined in vacuum.
\(\textbf{Final answer:}\)
\[
\boxed{\lambda_{P,\mathrm{glass}}=300\,\mathrm{nm},\quad\lambda_{Q,\mathrm{glass}}\approx233\,\mathrm{nm},\quad K_{\max,Q}\approx0.443\,\mathrm{eV}}
\]
616. Two models describe electronic angular momentum in hydrogen.
In the elementary Bohr model, the \(n=2\) stationary circular orbit has angular momentum magnitude \(L_{\mathrm{Bohr}}=n\hbar\).
In the quantum mechanical orbital model, the magnitude of orbital angular momentum is \(L_{\mathrm{orb}}=\sqrt{l(l+1)}\,\hbar\), where \(l\) is the azimuthal quantum number.
Ignore electron spin when evaluating orbital angular momentum, and use the elementary hydrogenic energy expression.
Which option correctly compares the Bohr second orbit with the quantum mechanical \(2s\) and \(2p\) orbitals?
ⓐ. All three have orbital angular momentum \(2\hbar\), because each has principal quantum number two.
ⓑ. The Bohr orbit has \(2\hbar\), \(2s\) has zero, and \(2p\) has \(\sqrt2\hbar\); the two orbitals have equal gross hydrogen energies.
ⓒ. The Bohr orbit has \(\sqrt2\hbar\), whereas both quantum mechanical orbitals have \(2\hbar\); their energies differ because of orbital shape.
ⓓ. The \(2s\) and \(2p\) orbital angular momenta are zero because electrons cannot possess orbital angular momentum in a stationary state.
Correct Answer: The Bohr orbit has \(2\hbar\), \(2s\) has zero, and \(2p\) has \(\sqrt2\hbar\); the two orbitals have equal gross hydrogen energies.
Explanation: \(\textbf{Evaluate the elementary Bohr angular momentum:}\)
Bohr's quantisation rule assigns
\[
L_{\mathrm{Bohr}}=n\hbar
\]
For the second orbit,
\[
L_{\mathrm{Bohr},2}=2\hbar
\]
This angular momentum is associated with the circular-orbit model.
\(\textbf{Evaluate the quantum mechanical }2s\textbf{ orbital:}\)
An \(s\) orbital has azimuthal quantum number
\[
l=0
\]
The quantum mechanical orbital angular momentum magnitude is
\[
L_{\mathrm{orb}}=\sqrt{l(l+1)}\,\hbar
\]
Therefore,
\[
L_{2s}=\sqrt{0(0+1)}\,\hbar
\]
\[
L_{2s}=0
\]
\(\textbf{Evaluate the quantum mechanical }2p\textbf{ orbital:}\)
A \(p\) orbital has
\[
l=1
\]
Thus,
\[
L_{2p}=\sqrt{1(1+1)}\,\hbar
\]
\[
L_{2p}=\sqrt2\,\hbar
\]
\(\textbf{Compare the electronic energies separately:}\)
For hydrogen in the elementary one-electron treatment,
\[
E_n=-\frac{13.6}{n^2}\,\mathrm{eV}
\]
Both \(2s\) and \(2p\) have \(n=2\).
Therefore,
\[
E_{2s}=E_{2p}=-\frac{13.6}{4}
\]
\[
E_{2s}=E_{2p}=-3.40\,\mathrm{eV}
\]
\(\textbf{Interpret the difference between the models:}\)
The principal quantum number in Bohr's circular-orbit rule is not interchangeable with the azimuthal quantum number in the quantum mechanical orbital-angular-momentum relation.
The \(2s\) and \(2p\) spatial states can have different orbital angular momenta while remaining degenerate in the elementary hydrogen energy model.
A zero value of orbital angular momentum for \(2s\) also does not mean that its electron lacks intrinsic spin.
The comparison demonstrates why replacing an orbital probability distribution by a sharply defined Bohr circular path changes more than the drawing of the electron's location.
\(\textbf{Final answer:}\)
\[
\boxed{L_{\mathrm{Bohr},2}=2\hbar,\qquad L_{2s}=0,\qquad L_{2p}=\sqrt2\,\hbar}
\]
617. An experimental ensemble contains equal numbers of separately prepared hydrogen atoms in the \(1s\) and \(2s\) states. Its position-density map is constructed by averaging the individual atomic probability densities:
\[
\rho_{\mathrm{ens}}(r)=\frac12\rho_{1s}(r)+\frac12\rho_{2s}(r)
\]
The \(2s\) wave function vanishes on its finite radial nodal sphere \(r=r_0\), while the \(1s\) wave function is nonzero at every finite radius.
Which option correctly predicts the ensemble density and its radial probability distribution at \(r_0\)?
ⓐ. Both must be zero because a radial node of one component is automatically a radial node of the combined ensemble.
ⓑ. The ensemble density is negative at \(r_0\) because the \(2s\) wave function changes sign there.
ⓒ. The ensemble density is positive, but the radial probability distribution must vanish because \(r_0\) is the radial-node position of \(2s\).
ⓓ. Both the ensemble density and its radial probability distribution are positive at \(r_0\), although the individual \(2s\) contribution is zero there.
Correct Answer: Both the ensemble density and its radial probability distribution are positive at \(r_0\), although the individual \(2s\) contribution is zero there.
Explanation: The ensemble is prepared as a statistical mixture of two kinds of hydrogen atoms.
Half occupy \(1s\) and half occupy \(2s\).
Its average local probability density is therefore the weighted sum of the separate orbital densities given in the stem.
The \(2s\) orbital has one finite spherical radial node.
At \(r=r_0\), its wave function vanishes.
Consequently,
\[
\rho_{2s}(r_0)=0
\]
The \(1s\) orbital has no finite radial node.
Its spatial probability density is positive at every finite radial distance.
Therefore,
\[
\rho_{1s}(r_0)\gt 0
\]
\(\textbf{Evaluate the combined local density:}\)
\[
\rho_{\mathrm{ens}}(r_0)
=\frac12\rho_{1s}(r_0)+\frac12(0)
\]
\[
\rho_{\mathrm{ens}}(r_0)=\frac12\rho_{1s}(r_0)\gt 0
\]
\(\textbf{Convert the ensemble density to radial probability:}\)
For a spherically symmetric density, the radial probability distribution is
\[
P(r)=4\pi r^2\rho(r)
\]
At the finite positive node radius,
\[
P_{\mathrm{ens}}(r_0)=4\pi r_0^2\frac12\rho_{1s}(r_0)
\]
Since \(r_0\gt 0\) and \(\rho_{1s}(r_0)\gt 0\),
\[
P_{\mathrm{ens}}(r_0)\gt 0
\]
\(\textbf{Interpret the result:}\)
A nodal surface belongs to a particular orbital wave function.
It is not automatically a nodal surface of a density formed by combining contributions from different occupied or prepared states.
The \(2s\) contribution vanishes at \(r_0\), but the \(1s\) contribution remains positive.
The ensemble therefore does not display the complete radial-density zero of the pure \(2s\) state at that radius.
This is an average of probabilities for separately prepared atoms, not an instruction to add their real wave-function amplitudes before squaring.
Confusing those two operations would incorrectly introduce interference between the separately prepared components.
The example distinguishes a pure orbital's nodal structure from the probability density observed in a mixed population.
\(\textbf{Final answer:}\)
\[
\rho_{\mathrm{ens}}(r_0)=\frac12\rho_{1s}(r_0)\gt 0,\qquad P_{\mathrm{ens}}(r_0)\gt 0
\]
618. An isolated hydrogen atom is described by both the elementary Bohr model and the quantum mechanical orbital model for principal quantum number \(n=3\).
A student draws the three orbitals \(3s\), \(3p\) and \(3d\) as three identical spherical probability boundaries of radius \(9a_0\), claiming that Bohr's third-orbit radius directly determines the \(90\%\)-probability boundary of every quantum mechanical orbital with \(n=3\).
Which option correctly evaluates the claim?
ⓐ. It is correct because equal hydrogenic orbital energies force identical spatial probability boundaries.
ⓑ. It is correct only for \(3d\), because a \(d\) orbital is always spherically symmetric in a one-electron atom.
ⓒ. It is incorrect; Bohr's \(9a_0\) is an orbit radius, not a shared \(90\%\) probability boundary for distinct \(3s\), \(3p\) and \(3d\) orbitals.
ⓓ. It is incorrect only because the \(3s\), \(3p\) and \(3d\) states have different energies even in the elementary hydrogen-like treatment.
Correct Answer: It is incorrect; Bohr's \(9a_0\) is an orbit radius, not a shared \(90\%\) probability boundary for distinct \(3s\), \(3p\) and \(3d\) orbitals.
Explanation: Bohr's radius relation for hydrogen is
\[
r_n=a_0n^2
\]
For \(n=3\), it gives
\[
r_3=9a_0
\]
This is the radius assigned to the third stationary circular orbit within Bohr's model.
The quantum mechanical model instead describes the electron through a spatial orbital wave function.
Its probability density is the squared magnitude of that wave function.
The \(3s\), \(3p\) and \(3d\) orbitals have the same principal quantum number but different azimuthal quantum numbers.
Their angular structures consequently differ.
The \(3s\) orbital is spherically symmetric and has two finite radial nodes.
A \(3p\) orbital has one angular node and one finite radial node.
A \(3d\) orbital has two angular nodes and no finite radial node.
Thus, their spatial probability distributions are not identical.
Within the elementary hydrogen-like model, their energies are nevertheless equal because the energy depends on \(n\).
Energy degeneracy does not require identical wave functions or orbital shapes.
A customary \(90\%\) boundary surface encloses a selected fraction of electron-position probability.
Its geometry must be related to the actual probability distribution.
The circular Bohr radius does not itself specify the location or geometry of that boundary.
In particular, the \(3p\) and \(3d\) orbital shapes are directional rather than spherically symmetric.
Representing all three by identical spherical boundaries at \(9a_0\) therefore confuses two distinct atomic models.
The legitimate conclusion is that equal \(n\) can imply equal gross electronic energy for hydrogen without implying one common, sharply defined electron trajectory or probability boundary.
619. The normalised ground-state probability density of a hydrogen-like one-electron ion follows the scaling relation
\[
\rho_Z(r)=Z^3\rho_1(Zr)
\]
where \(\rho_1\) is the hydrogen \(1s\) probability density, and distances are expressed in the same units. A spherical boundary of radius \(R\) encloses \(90\%\) of the electron probability in hydrogen.
Consider the corresponding \(1s\) state of \(\mathrm{He^+}\), neglecting reduced-mass effects. Which option correctly gives its \(90\%\)-probability radius, compares the local densities at the corresponding positions \(R\) and \(R/2\), and compares the probabilities in shells of thickness \(\Delta r\) at \(R\) and \(\Delta r/2\) at \(R/2\)?
ⓐ. Radius \(R/2\), density ratio \(8\), and equal thin-shell probabilities for the paired hydrogen and \(\mathrm{He^+}\) regions.
ⓑ. Radius \(R/2\); local density ratio \(4\); the helium-ion shell has twice the hydrogen-shell probability.
ⓒ. Radius \(R/4\); local density ratio \(8\); the two corresponding thin shells have equal approximate probabilities.
ⓓ. Radius \(2R\); local density ratio \(1/8\); the helium-ion shell has one-eighth the hydrogen-shell probability.
Correct Answer: Radius \(R/2\), density ratio \(8\), and equal thin-shell probabilities for the paired hydrogen and \(\mathrm{He^+}\) regions.
Explanation: \(\textbf{Apply the nuclear-charge scaling of the density:}\)
For hydrogen,
\[
Z_{\mathrm H}=1
\]
For the one-electron helium ion,
\[
Z_{\mathrm{He^+}}=2
\]
The supplied scaling law becomes
\[
\rho_{\mathrm{He^+}}(r)=8\rho_{\mathrm H}(2r)
\]
\(\textbf{Compare densities at corresponding scaled radii:}\)
At the helium-ion position \(r=R/2\),
\[
\rho_{\mathrm{He^+}}(R/2)=8\rho_{\mathrm H}(R)
\]
Therefore,
\[
\frac{\rho_{\mathrm{He^+}}(R/2)}{\rho_{\mathrm H}(R)}=8
\]
\(\textbf{Determine the probability enclosed by a scaled sphere:}\)
For a spherical density, the enclosed probability is
\[
F_Z(r)=4\pi\int_0^r r'^2\rho_Z(r')\,dr'
\]
Using the supplied scaling relation, the substitution \(u=Zr'\) gives
\[
F_Z(r)=F_1(Zr)
\]
Thus, corresponding radii related by the factor \(1/Z\) enclose equal probabilities.
Because
\[
F_1(R)=0.90
\]
the helium-ion sphere satisfying the same condition obeys
\[
F_2(R/2)=F_1(R)
\]
\[
F_2(R/2)=0.90
\]
Therefore, its \(90\%\)-probability radius is \(R/2\).
\(\textbf{Compare the corresponding thin-shell volumes:}\)
For a sufficiently thin spherical shell,
\[
\Delta V\approx4\pi r^2\Delta r
\]
The hydrogen shell has radius \(R\) and thickness \(\Delta r\).
The corresponding helium-ion shell has radius \(R/2\) and thickness \(\Delta r/2\).
Their volume ratio is
\[
\frac{\Delta V_{\mathrm{He^+}}}{\Delta V_{\mathrm H}}
=\frac{(R/2)^2(\Delta r/2)}{R^2\Delta r}
\]
\[
\frac{\Delta V_{\mathrm{He^+}}}{\Delta V_{\mathrm H}}=\frac18
\]
\(\textbf{Combine volume and density changes:}\)
The corresponding helium-ion density is eight times greater.
Its shell volume is one-eighth as large.
Therefore,
\[
\frac{\Delta P_{\mathrm{He^+}}}{\Delta P_{\mathrm H}}
=8\left(\frac18\right)
\]
\[
\frac{\Delta P_{\mathrm{He^+}}}{\Delta P_{\mathrm H}}=1
\]
\(\textbf{Interpret the probability scaling:}\)
The stronger nuclear attraction contracts the hydrogen-like \(1s\) probability distribution.
The local density rises as the occupied spatial region contracts.
However, the corresponding scaled spherical regions contain equal integrated probabilities.
Thus, a smaller boundary radius and a greater local density are consistent with normalisation.
The result uses the complete spatial scaling of the density rather than equating a Bohr orbit radius directly with an orbital boundary.
\(\textbf{Final answer:}\)
\[
\boxed{R_{90,\mathrm{He^+}}=\frac R2,\qquad\frac{\rho_{\mathrm{He^+}}(R/2)}{\rho_{\mathrm H}(R)}=8,\qquad\frac{\Delta P_{\mathrm{He^+}}}{\Delta P_{\mathrm H}}=1}
\]
620. An electron beam and a neutron beam initially have the same de Broglie wavelength, \(0.200\,\mathrm{nm}\), although their particle masses differ greatly.
Both beams then enter separate regions containing the same uniform electrostatic accelerating field. The electron travels through a potential difference chosen to make its final kinetic energy four times its initial kinetic energy. The neutron travels through an equivalent field region without other interactions.
Assume non-relativistic motion, the neutron's zero electric charge and the electron relation
\[
\lambda_e(\mathrm{nm})=\frac{1.227}{\sqrt{K_e(\mathrm{eV})}}
\]
Which option correctly gives the electron accelerating potential difference, the final de Broglie wavelength ratio \(\lambda_n/\lambda_e\), and the neutron's response?
ⓐ. Approximately \(37.6\,\mathrm{V}\); \(\lambda_n/\lambda_e=4\); the neutron accelerates because it possesses momentum.
ⓑ. Approximately \(112.9\,\mathrm{V}\); \(\lambda_n/\lambda_e=2\); the neutron wavelength remains unchanged.
ⓒ. Approximately \(112.9\,\mathrm{V}\); \(\lambda_n/\lambda_e=4\); both particles gain equal kinetic energy.
ⓓ. Approximately \(150.5\,\mathrm{V}\); \(\lambda_n/\lambda_e=2\); the neutron wavelength halves because it also possesses matter-wave character.
Correct Answer: Approximately \(112.9\,\mathrm{V}\); \(\lambda_n/\lambda_e=2\); the neutron wavelength remains unchanged.
Explanation: \(\textbf{Infer the electron's initial kinetic energy:}\)
The initial electron de Broglie wavelength is
\[
\lambda_{e,i}=0.200\,\mathrm{nm}
\]
Using the supplied relation,
\[
K_{e,i}=\left(\frac{1.227}{\lambda_{e,i}(\mathrm{nm})}\right)^2\mathrm{eV}
\]
Substituting,
\[
K_{e,i}=\left(\frac{1.227}{0.200}\right)^2
\]
\[
K_{e,i}\approx37.64\,\mathrm{eV}
\]
\(\textbf{Apply the changed electron kinetic energy:}\)
The final energy is four times the initial value:
\[
K_{e,f}=4K_{e,i}
\]
\[
K_{e,f}\approx4(37.64)
\]
\[
K_{e,f}\approx150.55\,\mathrm{eV}
\]
The kinetic-energy gain is
\[
\Delta K_e=K_{e,f}-K_{e,i}
\]
\[
\Delta K_e\approx150.55-37.64
\]
\[
\Delta K_e\approx112.91\,\mathrm{eV}
\]
\(\textbf{Determine the accelerating potential difference:}\)
For an electron accelerated through an appropriate potential difference of magnitude \(V\),
\[
\Delta K_e=eV
\]
Expressed in electronvolts,
\[
V\approx112.9\,\mathrm{V}
\]
\(\textbf{Determine the electron's new wavelength:}\)
For a non-relativistic electron,
\[
\lambda_e\propto\frac1{\sqrt{K_e}}
\]
Therefore,
\[
\frac{\lambda_{e,f}}{\lambda_{e,i}}=\sqrt{\frac{K_{e,i}}{K_{e,f}}}
\]
\[
\frac{\lambda_{e,f}}{\lambda_{e,i}}=\frac12
\]
\[
\lambda_{e,f}=0.100\,\mathrm{nm}
\]
\(\textbf{Evaluate the neutron's response independently:}\)
The neutron possesses zero net electric charge.
Under the stated ideal conditions, the electrostatic field does not accelerate it.
Its central momentum magnitude therefore remains unchanged.
Consequently,
\[
\lambda_{n,f}=0.200\,\mathrm{nm}
\]
\(\textbf{Compare the final matter wavelengths:}\)
\[
\frac{\lambda_{n,f}}{\lambda_{e,f}}=\frac{0.200}{0.100}
\]
\[
\frac{\lambda_{n,f}}{\lambda_{e,f}}=2
\]
\(\textbf{Interpret the different physical principles:}\)
Both electrons and neutrons exhibit matter-wave behaviour because de Broglie's relation applies to moving material particles.
However, their response to an electrostatic accelerating field depends on electric charge.
The neutron does not lose its matter-wave character merely because its wavelength remains unchanged.
The electron's shorter final wavelength results from increased momentum, whereas the neutron retains its original momentum under the stipulated conditions.
This separates the general existence of matter waves from the specific force used to change a particle's motion.
\(\textbf{Final answer:}\)
\[
\boxed{V\approx112.9\,\mathrm{V},\qquad\lambda_{e,f}=0.100\,\mathrm{nm},\qquad\frac{\lambda_{n,f}}{\lambda_{e,f}}=2}
\]