Hi,
I'm working on redox potential calculation of some organic molecules by DFT methods.
I found several articles and tutorials that recommend to use Born-Haber Cycle. However, I am curious about an experimental detail in the computation.
In a tutorial I found: http://ursula.chem.yale.edu/~batista/classes/tutorials/redoxpotentials.pdf. It suggest that I should compute the solvation energy by doing an energy calculation using the optimized geometry in gas phase.
In this point, I'm curious if we should do a structure optimization to acquire the solvation energy. From my understanding, the molecule structure will change after dissolved in certain solvents. Without structure optimization, the energy can be very different.
Dear Wenda Wu ,
Some years ago I have been computing redox potential (either reduction or oxidation) following the procedure described in this paper:
Article Computational Prediction of One-Electron Reduction Potential...
I hope this could help you in your work!
A possible way is calculating and comparing the so-called absolute redox potentials from the thermochemical data. We have published a couple of papers including this topic for metal 1,2-dichalcogenolene complexes:
1) https://pubs.rsc.org/en/content/articlelanding/2016/NJ/C6NJ01854H
2) Article Diradical Character of Neutral Heteroleptic Bis(1,2-dithiole...
For the former paper, details are reported in ESI.
A good starting point is the following paper:
Article Benchmark Calculations of Absolute Reduction Potential of Fe...
I hope this may help.
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