\(\mathrm{A}\) biradical is prepared with its two electrons in a singlet state. A magnetic field is present, and because the two electrons are in different environments their interaction with the field is \(\left(\mu_{\mathrm{B}} / \hbar\right) \mathscr{B}\left(g_{1} s_{1 z}+g_{2} s_{2 z}\right)\) with \(g_{1} \neq g_{2} .\) Evaluate the time-dependence of the probability that the electron spins will acquire a triplet configuration (that is, the probability that the \(S=1, M_{s}=0\) state will be populated). Examine the role of the energy separation \(h J\) of the singlet state and the \(M_{S}=0\) state of the triplet. Suppose \(g_{1}-g_{2}\) \(\approx 1 \times 10^{-3}\) and \(J \approx 0 ;\) how long does it take for the triplet state to emerge when \(\mathscr{B}=1.0 \mathrm{T}\) ? Hint. Use eqn 6.63 ; take \(|0,0\rangle=\left(1 / 2^{1 / 2}\right)(\alpha \beta-\beta \alpha)\) and \(|1,0\rangle=\left(1 / 2^{1 / 2}\right)(\alpha \beta+\beta \alpha) .\) See Problem 4.26 for the significance of \(\mu_{\mathrm{B}}\) and \(g\)

Short Answer

Expert verified
The step-by-step solution shows how to calculate the time for the system to evolve into the triplet state. To get a numeric value, the equation derived in step 4 must be evaluated with the given values.

Step by step solution

01

Write down the given states

Define the states. The initial singlet state is:|0,0> = (1 / \sqrt{2})( \alpha \beta - \beta \alpha )The final triplet state is:|1,0> = (1 / \sqrt{2})( \alpha \beta + \beta \alpha )
02

Calculate the transition amplitude

The transition amplitude between these states is then given by the matrix element:A = <1,0|H|0,0> = (1 / 2)(g_1 - g_2)\mu_B B, where H is the Hamiltonian of the system given in the problem.
03

Evaluate the time-dependent probability

To find the time-dependent probability for the system to be in the triplet state, we use the formulaP(t) = |<1,0|exp(-iHt)|0,0>|^2 = |<1,0|exp(-iHt/\hbar)|0,0>|^2 = |A|^2* t^2 / \hbar^2, Here we plug the transition amplitude obtained from step 2 into the equation.
04

Calculate time for the system to evolve into triplet state

Now, to find the time it takes for the system to evolve into the triplet state, rearrange the latter equation for time and insert the values given in the problem, including \( g_{1}-g_{2}\approx 1 \times 10^{-3} \), \( J \approx 0 \) , and \( \mathscr{B}=1.0 T \) .

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Most popular questions from this chapter

Repeat the last problem but set \(H_{\mathrm{s}, \mathrm{s}}=\gamma\) and \(S_{\mathrm{s}^{\prime}} \neq 0\) Evaluate the overlap integrals between 1 s-orbitals on centres separated by \(R ;\) use $$S=\left\\{1+\frac{R}{a_{0}}+\frac{1}{3}\left(\frac{R}{a_{0}}\right)^{2}\right\\} \mathrm{e}^{-R / a_{0}}$$ Suppose that \(\beta / \gamma=S_{\mathrm{s}, \mathrm{s}_{2}} / S_{\mathrm{s}, \mathrm{s}} .\) For a numerical result, take \(R=80 \mathrm{pm}, a_{0}=53 \mathrm{pm}\)

Suppose that the potential energy of a particle on a ring depends on the angle \(\varphi\) as \(H^{(1)}=\varepsilon \sin ^{2} \varphi .\) Calculate the first- order corrections to the energy of the degenerate \(m_{l}=\pm 1\) states, and find the correct linear combinations for the perturbation calculation. Find the second-order correction to the energy. Hint. This is an example of degenerate-state perturbation theory, and so find the correct linear combinations by solving eqn 6.42 after deducing the energies from the roots of the secular determinant. For the matrix elements, express \(\sin \varphi\) as \((1 / 2 \mathrm{i})\left(\mathrm{e}^{\mathrm{i} \varphi}-\mathrm{e}^{-\mathrm{i} \varphi}\right)\) When evaluating eqn \(6.42,\) do not forget the \(m_{1}=0\) state lying beneath the degenerate pair. The energies are equal to \(m_{l}^{2} \hbar^{2} / 2 m r^{2} ;\) use \(\psi_{m_{l}}=(1 / 2 \pi)^{1 / 2} \mathrm{e}^{i m_{\mu} \varphi}\) for the unperturbed states.

Find the complete dependence of the \(A\) and \(B\) coefficients on atomic number for the \(2 \mathrm{p} \rightarrow 1\) s transitions of hydrogenic atoms. Calculate how the stimulated emission rate depends on \(Z\) when the atom is exposed to black-body radiation at \(1000 \mathrm{K} .\) Hint. The relevant density of states also depends on \(Z\).

Calculate the second-order energy correction to the ground state of a particle in a one-dimensional box for a perturbation of the form \(H^{(1)}=-\varepsilon \sin (\pi x / L)\) by using the closure approximation. Infer a value of \(\Delta E\) by comparison with the numerical calculation in Example \(6.4 .\) These two problems \((6.14 \text { and } 6.15)\) show that the parameter \(\Delta E\) depends on the perturbation and is not simply a characteristic of the system itself.

A simple calculation of the energy of the helium atom supposes that each electron occupies the same hydrogenic 1 s-orbital (but with \(Z=2\) ). The electronelectron interaction is regarded as a perturbation, and calculation gives $$\int \psi_{1 s}^{2}\left(r_{1}\right)\left(\frac{e^{2}}{4 \pi \varepsilon_{0} r_{12}}\right) \psi_{1 s}^{2}\left(r_{2}\right) \mathrm{d} \tau=\frac{5}{4}\left(\frac{e^{2}}{4 \pi \varepsilon_{0} a_{0}}\right)$$ (see Example 7.2 ). Estimate (a) the binding energy of helium, (b) its first ionization energy. Hint. Use eqn 6.15 with \(E_{1}=E_{2}=E_{1 \mathrm{s}} .\) Be careful not to count the electronelectron interaction energy twice.

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