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If \(\tau_{f}=1 \times 10^{-10} \mathrm{s}\) and \(k_{i c}=5 \times 10^{8} \mathrm{s}^{-1},\) what is \(\phi_{f} ?\) Assume that the rate constants for intersystem crossing and quenching are sufficiently small that these processes can be neglected.

Short Answer

Expert verified
Answer: The fluorescence quantum yield for the given molecule is approximately 0.0476, which means about 4.76% of the absorbed photons are emitted as fluorescence photons.

Step by step solution

01

Write down the given values

We have the following values given: - Fluorescence lifetime, \(\tau_{f} = 1 \times 10^{-10}\ \mathrm{s}\) - Rate of radiative decay, \(k_{i c} = 5 \times 10^{8}\ \mathrm{s}^{-1}\)
02

Write down the formula for fluorescence quantum yield

We will be using the formula: $$\phi_{f} = \frac{k_{i c} \tau_{f}}{1 + k_{i c} \tau_{f}}$$
03

Plug in the given values and solve for \(\phi_{f}\)

Now, we will substitute the given values for \(\tau_{f}\) and \(k_{i c}\) in the formula: $$\phi_{f} = \frac{(5 \times 10^{8}\ \mathrm{s}^{-1})(1 \times 10^{-10}\ \mathrm{s})}{1 + (5 \times10^{8}\ \mathrm{s}^{-1})(1 \times 10^{-10}\ \mathrm{s})}$$
04

Perform the calculations

Calculate the numerator and denominator separately: Numerator: $$(5 \times 10^{8}\ \mathrm{s}^{-1})(1 \times 10^{-10}\ \mathrm{s}) = 5 \times 10^{-2}$$ Denominator: $$1+ (5 \times 10^{8}\ \mathrm{s}^{-1})(1 \times 10^{-10}\ \mathrm{s}) = 1 + 5 \times 10^{-2} = 1.05$$ Now, calculate \(\phi_{f}\): $$\phi_{f} =\frac{5 \times 10^{-2}}{1.05} \approx 0.0476$$
05

Interpret the result

The fluorescence quantum yield, \(\phi_{f}\), is approximately 0.0476. This value represents the efficiency with which absorbed photons are emitted as fluorescence photons. In this case, about 4.76% of the absorbed photons are emitted as fluorescence.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Fluorescence Lifetime
Fluorescence lifetime, denoted by \(\tau_f\), is a parameter that represents the average time a molecule remains in its excited state before returning to the ground state via fluorescence. This concept is crucial in understanding how quickly fluorescence occurs. A longer \(\tau_f\) indicates that the excited state is relatively stable and that emitted photons are released over a longer period.

In practical terms, fluorescence lifetime is measured in nanoseconds (ns), and it's affected by various factors, such as the molecular structure of the fluorophore, the solvent, and temperature. In the given exercise, we're working with a fluorescence lifetime of \(1 \times 10^{-10}\) seconds, which suggests a very fast fluorescence process.

It's important to note that fluorescence lifetime doesn't give us a direct measure of fluorescence efficiency; it only tells us about the duration of fluorescence. However, it is directly related to both non-radiative and radiative decay rates, which leads us to our next concept.
Radiative Decay Rate
The radiative decay rate, represented as \(k_{ic}\), is the probability per unit time of the excited state returning to the ground state by emitting a photon, which in effect contributes to fluorescence. Therefore, it provides an indication of how likely it is for fluorescence to occur compared to other non-radiative processes such as heat loss.

The rate is typically measured in reciprocal seconds (\(s^{-1}\)) and can vary widely depending on the nature of the fluorescent molecule and its environment. A higher radiative decay rate suggests a greater propensity for a molecule to fluoresce.

In our exercise, the radiative decay rate is \(5 \times 10^{8}\ \mathrm{s}^{-1}\). This signifies a strong likelihood of fluorescence occurring rapidly once the molecule is excited. The radiative decay rate plays a pivotal role in the quantum yield calculation as illustrated in our exercise solution.
Quantum Yield Calculation
The quantum yield of fluorescence, symbolized by \(\phi_f\), is the ratio of the number of photons emitted to the number of photons absorbed. This yield is a dimensionless number ranging from 0 to 1, representing the fluorescence efficiency of a molecule.

For the calculation of the quantum yield, we employ the formula:
\[\phi_{f} = \frac{k_{i c} \tau_{f}}{1 + k_{i c} \tau_{f}}\]
This shows us that the quantum yield is dependent on both the fluorescence lifetime \(\tau_{f}\) and the radiative decay rate \(k_{i c}\). The operation is as follows: calculate the product of \(k_{i c}\) and \(\tau_{f}\), and then divide this product by the sum of 1 and the same product.

Within the context of our exercise, we performed these calculations and found that the quantum yield is approximately 0.0476, indicating that under the given conditions, around 4.76% of the absorbed photons result in fluorescence. This value helps assess the effectiveness of fluorescence and is particularly important in fields like photochemistry and photobiology, where the understanding of light-matter interactions is essential.
When considering improvements to the exercise, it's crucial to explain the physical meaning of each term and the relevance of quantum yield in practical applications, such as in the design of fluorescent probes for biological imaging.

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Most popular questions from this chapter

Consider the gas-phase isomerization of cyclopropane: Are the following data of the observed rate constant as a function of pressure consistent with the Lindemann mechanism? $$\begin{array}{cccc} \boldsymbol{P}(\text { Torr }) & \boldsymbol{k}\left(\mathbf{1 0}^{4} \mathbf{s}^{-1}\right) & \boldsymbol{P}(\text { Torr }) & \boldsymbol{k}\left(\mathbf{1 0}^{4} \mathbf{s}^{-1}\right) \\ \hline 84.1 & 2.98 & 1.36 & 1.30 \\ 34.0 & 2.82 & 0.569 & 0.857 \\ 11.0 & 2.23 & 0.170 & 0.486 \\ 6.07 & 2.00 & 0.120 & 0.392 \\ 2.89 & 1.54 & 0.067 & 0.303 \end{array}$$

In the discussion of the Lindemann mechanism, it was assumed that the rate of activation by collision with another reactant molecule \(A\) was the same as collision with a nonreactant molecule M such as a buffer gas. What if the rates of activation for these two processes are different? In this case, the mechanism becomes \\[ \begin{array}{l} \mathrm{A}+\mathrm{M} \quad \underbrace{k_{1}}{=} \mathrm{A}^{*}+\mathrm{M} \\\ \mathrm{A}+\mathrm{A} \stackrel{k_{-1}}{=} \mathrm{k}_{-2} \\ \mathrm{A}^{*} \stackrel{\mathrm{k}_{3}}{\longrightarrow} \mathrm{P} \end{array} \\] a. Demonstrate that the rate law expression for this mechanism is \\[ R=\frac{k_{3}\left(k_{1}[\mathrm{A}][\mathrm{M}]+k_{2}[\mathrm{A}]^{2}\right)}{k_{-1}[\mathrm{M}]+k_{-2}[\mathrm{A}]+k_{-3}} \\] b. Does this rate law reduce to the expected form when \([\mathrm{M}]=0 ?\)

For phenanthrene, the measured lifetime of the triplet state \(\tau_{p}\) is \(3.3 \mathrm{s}\), the fluorescence quantum yield is \(0.12,\) and the phosphorescence quantum yield is 0.13 in an alcohol-ether glass at \(77 \mathrm{K}\). Assume that no quenching and no internal conversion from the singlet state occurs. Determine \(k_{p}, k_{i s c}^{T},\) and \(k_{i s c}^{S} / k_{f}\)

An experiment is performed in which the rate constant for electron transfer is measured as a function of dis- tance by attaching an electron donor and acceptor to pieces of DNA of varying length. The measured rate constant for electron transfer as a function of separation distance is as follows: $$\begin{array}{lcccc} \boldsymbol{k}_{e x p}\left(\mathbf{s}^{-1}\right) & 2.10 \times 10^{8} & 2.01 \times 10^{7} & 2.07 \times 10^{5} & 204 \\ \text { Distance (脕) } & 14 & 17 & 23 & 32 \end{array}$$ a. Determine the value for \(\beta\) that defines the dependence of the electron transfer rate constant on separation distance. b. It has been proposed that DNA can serve as an electron \(" \pi\) -way" facilitating electron transfer over long distances. Using the rate constant at 17 脕 presented in the table, what value of \(\beta\) would result in the rate of electron transfer decreasing by only a factor of 10 at a separation distance of \(23 \AA ?\)

In Marcus theory for electron transfer, the reorganization energy is partitioned into solvent and solute contributions. Modeling the solvent as a dielectric continuum, the solvent reorganization energy is given by \\[ \lambda_{s o l}=\frac{(\Delta e)^{2}}{4 \pi \varepsilon_{0}}\left(\frac{1}{d_{1}}+\frac{1}{d_{2}}-\frac{1}{r}\right)\left(\frac{1}{n^{2}}-\frac{1}{\varepsilon}\right) \\] where \(\Delta e\) is the amount of charge transferred, \(d_{1}\) and \(d_{2}\) are the ionic diameters of ionic products, \(r\) is the separation distance of the reactants, \(n^{2}\) is the index of refraction of the surrounding medium, and \(\varepsilon\) is the dielectric constant of the medium. In \\[ \text { addition, }\left(4 \pi \varepsilon_{0}\right)^{-1}=8.99 \times 10^{9} \mathrm{Jm} \mathrm{C}^{-2} \\] a. For an electron transfer in water \((n=1.33 \text { and } \varepsilon=80 .)\) where the ionic diameters of both species are \(6 \AA\) and the separation distance is \(15 \AA\), what is the expected solvent reorganization energy? b. Redo the earlier calculation for the same reaction occurring in a protein. The dielectric constant of a protein is dependent on sequence, structure, and the amount of included water; however, a dielectric constant of 4 is generally assumed consistent with a hydrophobic environment. Using light-scattering measurements the dielectric constant of proteins has been estimated to be \(\sim 1.5\)

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