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I'm thinking about doing some computational research about pyrazoline oxidation in chlorinated solvents under light. I've found plausible mechanism (article) that involves single electron transfer from the molecule of pyrazoline to dichloroethane (DCE).

Pyrazoline oxydation mechanism

My main concern is about the second step, as there is electron transfer and change in multiplicity. I'm thinking about broken-symmetry DFT or multi-rerference methods, but I have no experience in them, so I'm not sure about it. What are the approaches to model such types of reactions? (I assume it has something to do with Marcus theory)

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    $\begingroup$ +1 But what is it that you want to model? The energy at each step of this sequence of reactions? The speed of each step? The probability that each step will occur? The nature of the wavefunction from step-to-step? $\endgroup$ Jan 25 at 19:26
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    $\begingroup$ If you are interested in learning about calculating rates of electrons transfer, check out this webinar on constrained DFT. $\endgroup$
    – Cody Aldaz
    Jan 25 at 19:38
  • $\begingroup$ @NikeDattani, let's say I want to have energy profile for entire reaction and transition states for each step. I'm not sure really, but I think it will help me to see how the substituents influence the reaction. $\endgroup$ Jan 26 at 11:40
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    $\begingroup$ Maybe this answer can get some light. $\endgroup$
    – Camps
    Jan 27 at 17:31
  • $\begingroup$ @Camps thank you a lot, it really helps to understand the idea. I'm concerned about the change of multiplicity and initial photo excitation of the pyrazoline molecule, maybe it would be singlet-triplet transition and I need to account for it somehow. $\endgroup$ Jan 28 at 7:37

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