Energy Transfer and rate equation

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SUMMARY

The discussion centers on the energy transfer rate constant in the reaction A* + C → A + C*, highlighting the confusion between first-order and second-order reaction classifications. The rate equation presented is d[A*]/dt = k_{C*→A}[A][C*] - k_{A*→C}[A*][C], indicating that energy transfer is a second-order reaction with k_{A*→C} having units of M-1s-1. The inconsistency arises from differing interpretations in literature, where some papers treat energy transfer as first-order, particularly in the context of Förster resonance energy transfer (FRET). The discussion emphasizes the importance of the reaction mechanism in determining the appropriate classification and units for the rate constants.

PREREQUISITES
  • Understanding of reaction kinetics, specifically second-order reactions.
  • Familiarity with Förster resonance energy transfer (FRET) principles.
  • Knowledge of rate equations and their units in chemical reactions.
  • Concepts of intramolecular and intermolecular energy transfer mechanisms.
NEXT STEPS
  • Research the differences between first-order and second-order reaction kinetics.
  • Study the Förster resonance energy transfer (FRET) equation and its applications.
  • Examine case studies on collisional versus resonance energy transfer mechanisms.
  • Explore literature on the interpretation of rate constants in energy transfer processes.
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Chemists, physicists, and researchers in photophysics or molecular biology who are investigating energy transfer mechanisms and their implications in various chemical reactions.

HAYAO
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What is the unit for energy transfer rate constant?

I am confused because of the order of reaction of energy transfer. Consider the case for following energy transfer A* + C → A + C*. The star represent excited state. Then the rate equation for A* would be as follows:
\frac{d[A^{*}]}{dt} = \frac{d[C]}{dt} = k_{C^{*}\rightarrow A}[A][C^{*}] -k_{A^{*}\rightarrow C}[A^{*}][C]
and you can see that energy transfer in this case is a second-order reaction.

If [A^{*}] is in unit of concentration M (mol l-1), obviously the unit for k_{A^{*}\rightarrow C} would be M-1 s-1. As so, units are different from typical photophysical process like fluorescence which is usually first order reaction. However, I have seen papers that treats energy transfer as first-order reaction (like this one), while I've seen ones that treats it as second-order reaction (like this one). Which one is right? I think that the latter is right, but then if you think about for example Forster transfer equation:
k_{A^{*}\rightarrow C} = \frac{9000c^{4}ln10}{128\pi ^{5}n^{4}N_{A}\tau _{0}^{a}}\cdot \frac{\kappa ^{2}}{R^{6}}\int f_{a}(\upsilon )\varepsilon _{b}(\upsilon )\frac{d\upsilon }{\upsilon ^{4}}
it is obvious that the unit is given as first-order reaction. Do you have to change the units into second-order reaction? If so, then how do you do that?
 
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Like the rate constants for chemical reactions, the units for the rate constant depends on the exact mechanism of energy transfer. Collisional energy transfer is a different process than resonance energy transfer, so why would you necessarily expect the rate constants to be comparable?
 
Ygggdrasil said:
Like the rate constants for chemical reactions, the units for the rate constant depends on the exact mechanism of energy transfer. Collisional energy transfer is a different process than resonance energy transfer, so why would you necessarily expect the rate constants to be comparable?
Because in the above two papers I have given as an example both considers the energy transfer to be in resonance mechanism. Despite so, both paper have different take on whether the transfer is first-order or second-order.
 
I think the equation for Förster resonance energy transfer assumes that the transfer occurs intramolecularly, especially because the equation requires defining the distance (R) between the transition dipoles as well as their relative orientation (κ2). Perhaps the difference between the two papers is whether they're considering intermolecular RET or intramolecular RET (again, the details of the exact mechanism are important).
 
Yes, that is what I thought. But both papers consider intramolecular RET, hence the reason I am confused.
 

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