IPhO 1988 · Theory problem 3

Recombination of Positive and Negative Ions in Ionized Gas

Introduction

A gas consists of positive ions of some element (at high temperature) and electrons. The positive ion belongs to an atom of unknown mass number \(Z\). It is known that this ion has only one electron in the shell (orbit).

Let this ion be represented by the symbol \(A^{(Z-1)+}\)

Constants:

Constant Value
electric field constant \(\displaystyle \varepsilon_0=8{,}85\cdot10^{-12}\ \frac{\mathrm{A\cdot s}}{\mathrm{V\cdot m}}\)
elementary charge \(\displaystyle e=\pm1{,}602\cdot10^{-19}\ \mathrm{A\cdot s}\)
\(\displaystyle q^2=\frac{e^2}{4\cdot\pi\cdot\varepsilon_0}=2{,}037\cdot10^{-28}\ \mathrm{J\cdot m}\)
Planck’s constant \(\displaystyle \hbar=1{,}054\cdot10^{-34}\ \mathrm{J\cdot s}\)
(rest) mass of an electron \(\displaystyle m_e=9{,}108\cdot10^{-31}\ \mathrm{kg}\)
Bohr’s atomic radius \(\displaystyle r_{\mathrm B}=\frac{\hbar}{m\cdot q^2}=5{,}92\cdot10^{-11}\ \mathrm m\)
Rydberg’s energy \(\displaystyle E_{\mathrm R}=\frac{q^2}{2\cdot r_{\mathrm B}}=2{,}180\cdot10^{-18}\ \mathrm J\)
(rest) mass of a proton \(\displaystyle m_{\mathrm p}\cdot c^2=1{,}503\cdot10^{-10}\ \mathrm J\)

Questions:

3.1

Assume that the ion which has just one electron left the shell.
\(A^{(Z-1)+}\) is in the ground state.

In the lowest energy state, the square of the average distance of the electron from the nucleus or \(r^2\) with components along x-, y- and z-axis being \((\Delta x)^2\), \((\Delta y)^2\) and \((\Delta z)^2\) respectively and \[ r_0^2=(\Delta x)^2+(\Delta y)^2+(\Delta z)^2 \] and also the square of the average momentum by \[ p_0^2=(\Delta p_x)^2+(\Delta p_y)^2+(\Delta p_z)^2, \] whereas \[ \Delta p_x\geq\frac{\hbar}{2\cdot\Delta x},\qquad \Delta p_y\geq\frac{\hbar}{2\cdot\Delta y} \quad\text{and}\quad \Delta p_z\geq\frac{\hbar}{2\cdot\Delta z}. \]

Write inequality involving \((p_0)^2\cdot(r_0)^2\) in a complete form.

3.2

The ion represented by \(A^{(Z-1)+}\) may capture an additional electron and consequently emits a photon.

Write down an equation which is to be used for calculation the frequency of an emitted photon.

3.3

Calculate the energy of the ion \(A^{(Z-1)+}\) using the value of the lowest energy. The calculation should be approximated based on the following principles:

3.3.A

The potential energy of the ion should be expressed in terms of the average value of \(\dfrac1r\).

(ie. \(\dfrac1{r_0}\); \(r_0\) is given in the problem).

3.3.B

In calculating the kinetic energy of the ion, use the average value of the square of the momentum given in 3.1 after being simplified by \[ (p_0)^2\cdot(r_0)^2\approx(\hbar)^2 \]

3.4

Calculate the energy of the ion \(A^{(Z-2)+}\) taken to be in the ground state, using the same principle as the calculation of the energy of \(A^{(Z-1)+}\). Given the average distance of each of the two electrons in the outermost shell (same as \(r_0\) given in 3.3) denoted by \(r_1\) and \(r_2\), assume the average distance between the two electrons is given by \(r_1+r_2\) and the average value of the square of the momentum of each electron obeys the principle of uncertainty ie. \[ p_1^2\cdot r_1^2\approx\hbar^2 \quad\text{and}\quad p_2^2\cdot r_2^2\approx\hbar^2 \]

hint: Make use of the information that in the ground state \(r_1=r_2\)

3.5

Consider in particular the ion \(A^{(Z-2)+}\) is at rest in the ground state when capturing an additional electron and the captured electron is also at rest prior to the capturing. Determine the numerical value of \(Z\), if the frequency of the emitted photon accompanying electron capturing is \(2{,}057\cdot10^{17}\ \mathrm{rad/s}\). Identify the element which gives rise to the ion.

Official English text of the problem.

Answers

Define the energy scale \[ \mathcal R=\frac{m_e(q^2)^2}{2\hbar^2}. \] With consistent constants, this is the Rydberg energy \(E_{\mathrm R}\). The printed constants are inconsistent, so their numerical consequences are distinguished below.

  • 3.1 \[ \boxed{ p_0^2r_0^2\geq \frac{\hbar^2}{4} \bigl[(\Delta x)^2+(\Delta y)^2+(\Delta z)^2\bigr] \left[\frac1{(\Delta x)^2}+\frac1{(\Delta y)^2}+\frac1{(\Delta z)^2}\right] \geq\frac94\hbar^2.} \]

  • 3.2 \[ \boxed{h\nu=\hbar\omega=E_i-E_f+K_i+K_e-K_f,} \] where \(E_i,E_f\) are internal electronic energies and the \(K\)’s are translational kinetic energies.

  • 3.3 \[ \boxed{E_1=-Z^2\mathcal R} \qquad\text{(conventionally, }-Z^2E_{\mathrm R}\text{).} \]

  • 3.3.A \[ \boxed{U_1(r_0)\approx-\frac{Zq^2}{r_0}.} \]

  • 3.3.B \[ \boxed{T_1(r_0)\approx\frac{\hbar^2}{2m_er_0^2},\qquad r_{0,\min}=\frac{\hbar^2}{m_eZq^2}.} \]

  • 3.4 \[ \boxed{ E_2=-2\left(Z-\frac14\right)^2\mathcal R,\qquad r_1=r_2=\frac{\hbar^2}{m_eq^2(Z-\frac14)}.} \]

  • 3.5 For the intended capture of a second electron, \[ \boxed{Z=\frac12+\sqrt{\frac{\hbar\omega}{\mathcal R}+\frac18}} \] with negligible recoil. The quoted \(E_{\mathrm R}\) gives \(Z=3.673\); the printed \(q^2,m_e,\hbar\) give \(Z=4.088\). Both have the nearest integer \[ \boxed{Z=4,\qquad \text{beryllium (Be)}.} \] This is a conditional, approximate identification. As printed, part 3.5 describes capture of a third electron, whose energy has not been specified.

Solution

The charge states imply a nucleus of charge \(+Ze\). We treat its mass as large compared with the electron mass, neglect its motion when calculating electronic energies, and use nonrelativistic electron kinetic energies. Electronic binding energies are measured relative to the nucleus and separated electrons.

3.1

Squaring and adding the three uncertainty inequalities gives \[ p_0^2\geq\frac{\hbar^2}{4} \left[\frac1{(\Delta x)^2}+\frac1{(\Delta y)^2}+\frac1{(\Delta z)^2}\right]. \]

Multiplication by the specified \(r_0^2\) gives the complete expression \[ \begin{aligned} p_0^2r_0^2\geq\frac{\hbar^2}{4}\biggl[ 3 &+\frac{(\Delta x)^2}{(\Delta y)^2} +\frac{(\Delta y)^2}{(\Delta x)^2}\\ &+\frac{(\Delta y)^2}{(\Delta z)^2} +\frac{(\Delta z)^2}{(\Delta y)^2}\\ &+\frac{(\Delta z)^2}{(\Delta x)^2} +\frac{(\Delta x)^2}{(\Delta z)^2} \biggr]. \end{aligned} \]

Each reciprocal pair is at least \(2\), since \(u+u^{-1}\geq2\) for \(u>0\). Hence \[ \boxed{p_0^2r_0^2\geq\frac94\hbar^2.} \]

Equality requires both equal spatial uncertainties, \[ \Delta x=\Delta y=\Delta z, \] and saturation of all three component uncertainty relations. Spherical symmetry alone does not establish saturation.

3.2

The radiative capture reaction is \[ A^{(Z-1)+}+e^-\longrightarrow A^{(Z-2)+}+\gamma. \]

Let \(E_i,E_f\) denote the initial and final internal electronic energies. Let \(K_i,K_e\) be the initial ion and electron kinetic energies, and \(K_f\) the final ion kinetic energy. Conservation of energy gives \[ E_i+K_i+K_e=E_f+K_f+\hbar\omega. \]

Thus \[ \boxed{\hbar\omega=h\nu=E_i-E_f+K_i+K_e-K_f,} \qquad \omega=2\pi\nu. \]

The common nuclear and electron rest energies cancel. Momentum conservation determines the final ion’s recoil. If the initial kinetic energies and recoil are negligible, this reduces to \[ \boxed{\hbar\omega\approx E_i-E_f.} \]

3.3

We now minimize the approximate total electronic energy required by the problem.

3.3.A

The attractive Coulomb potential is \[ U(r)=-\frac{Ze^2}{4\pi\varepsilon_0r} =-\frac{Zq^2}{r}. \] Using the prescribed approximation to its expectation value, \[ \boxed{U_1\approx-Zq^2\left\langle\frac1r\right\rangle \approx-\frac{Zq^2}{r_0}.} \]

3.3.B

The electron has zero mean momentum in the stationary ground state, so its mean squared momentum is represented by \(p_0^2\). The stipulated estimate \[ p_0^2r_0^2\approx\hbar^2 \] therefore gives \[ \boxed{T_1\approx\frac{p_0^2}{2m_e} \approx\frac{\hbar^2}{2m_er_0^2}.} \]

This is a deliberately coarse replacement of the uncertainty result: it discards the numerical coefficient from 3.1 and is not an equality derived from that bound.

The estimated total energy is consequently \[ E_1(r_0)=\frac{\hbar^2}{2m_er_0^2}-\frac{Zq^2}{r_0}. \] Its stationary point satisfies \[ \frac{dE_1}{dr_0} =-\frac{\hbar^2}{m_er_0^3} +\frac{Zq^2}{r_0^2}=0, \] giving \[ \boxed{r_{0,\min}=\frac{\hbar^2}{m_eZq^2}.} \]

The second derivative there is \(\hbar^2/(m_er_0^4)>0\), so this is a minimum. Substitution yields \[ T_{1,\min}=\frac{m_eZ^2(q^2)^2}{2\hbar^2}, \qquad U_{1,\min}=-\frac{m_eZ^2(q^2)^2}{\hbar^2}, \] and hence \[ \boxed{E_1=-\frac{m_eZ^2(q^2)^2}{2\hbar^2}=-Z^2\mathcal R.} \]

With consistent Bohr and Rydberg constants, these are the familiar forms \[ r_{0,\min}=\frac{r_{\mathrm B}}Z, \qquad E_1=-Z^2E_{\mathrm R}. \]

3.4

There are now two electron kinetic energies, two attractive electron–nucleus terms, and one repulsive electron–electron term. Under the prescribed separation approximation, \[ E_2(r_1,r_2)= \frac{\hbar^2}{2m_e}\left(\frac1{r_1^2}+\frac1{r_2^2}\right) -Zq^2\left(\frac1{r_1}+\frac1{r_2}\right) +\frac{q^2}{r_1+r_2}. \]

Using the given ground-state condition \(r_1=r_2=r\), \[ E_2(r)=\frac{\hbar^2}{m_er^2} -\frac{2Zq^2}{r}+\frac{q^2}{2r} =\frac{\hbar^2}{m_er^2} -\frac{2q^2(Z-\frac14)}r. \]

Minimization gives \[ -\frac{2\hbar^2}{m_er^3} +\frac{2q^2(Z-\frac14)}{r^2}=0, \] so \[ \boxed{r=\frac{\hbar^2}{m_eq^2(Z-\frac14)}.} \]

At this radius, \[ \boxed{ E_2=-\frac{m_e(q^2)^2}{\hbar^2} \left(Z-\frac14\right)^2 =-2\mathcal R\left(Z-\frac14\right)^2.} \]

Thus, in this model, electron repulsion replaces \(Z\) by the effective value \(Z-\tfrac14\) in each electron’s ground-state energy.

3.5

To connect this part with the energies calculated in 3.3 and 3.4, the capture must be interpreted as \[ A^{(Z-1)+}+e^-\longrightarrow A^{(Z-2)+}+\gamma. \] The literal charge state printed in 3.5 instead describes a different process: capture of a third electron, whose energy is not calculated in this problem.

For the intended process, the released binding energy is \[ \begin{aligned} \Delta E&=E_1-E_2\\ &=\left[2\left(Z-\frac14\right)^2-Z^2\right]\mathcal R\\ &=\boxed{\left(Z^2-Z+\frac18\right)\mathcal R}. \end{aligned} \]

Although both incoming particles are at rest, the final ion must recoil. If its mass is \(M\), momentum conservation gives \[ p_{\mathrm{ion}}=p_\gamma=\frac{\hbar\omega}{c}. \] Consequently, \[ \Delta E=\hbar\omega+\frac{(\hbar\omega)^2}{2Mc^2}. \]

The supplied frequency is an angular frequency, so the photon energy is \[ E_\gamma=\hbar\omega =(1.054\times10^{-34})(2.057\times10^{17}) =\boxed{2.168\times10^{-17}\ \mathrm J}. \]

Using \(Mc^2\geq m_pc^2\), the fractional recoil correction is bounded by \[ \frac{K_{\mathrm{recoil}}}{E_\gamma} =\frac{E_\gamma}{2Mc^2} \leq\frac{2.168\times10^{-17}}{2(1.503\times10^{-10})} =7.21\times10^{-8}. \] It is entirely negligible at the precision of the data.

Therefore \[ Z^2-Z+\frac18=\frac{\hbar\omega}{\mathcal R}, \] whose physical root is \[ \boxed{Z=\frac12+\sqrt{\frac{\hbar\omega}{\mathcal R}+\frac18}.} \]

The inconsistent constants lead to two numerical estimates:

Constants used for the energy scale \(\mathcal R\) Estimated \(Z\)
Quoted Rydberg energy \(E_{\mathrm R}\) \(2.180\times10^{-18}\ \mathrm J\) \(3.673\)
Printed \(q^2,m_e,\hbar\), through \(m_e(q^2)^2/(2\hbar^2)\) \(1.701\times10^{-18}\ \mathrm J\) \(4.088\)

Both estimates have the nearest integer \(4\). Accordingly, under the intended capture interpretation and the approximate model, the inferred element is \[ \boxed{Z=4,\qquad \text{beryllium},} \] with capture \[ \mathrm{Be}^{3+}+e^-\longrightarrow\mathrm{Be}^{2+}+\gamma. \]

The supplied text does not support an exact, internally consistent integer determination.

The solution was checked against the official solution.