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#1 Yesterday 03:24:00

wham09
Member
Registered: 2025-09-19
Posts: 50

Adjusting halogen radius for geometry optimization

Dear Prof. Lu,

I am calculating a toluene-solvated organometallic transition state that contain half-cleaved palladium-bromide bond. I was optimizing the geometry of this TS using PBE0-D3(BJ)/ma-SVP (PCM, toluene) level of theory, and observed oscillating behavior.

Out of curiosity, I modified the PCM radius of bromine atom to 2.60 by using modifysph command, which is what was done in Truhlar's SMD18 paper (https://doi.org/10.1002/chem.201803652).

Of course, what Truhlar did was optimizing the geometries of his compounds using M06-2X/def2-TZVP (def2-TZVPD for bromine). I knew this, but I still chose to optimize my compound using PBE0-D3(BJ)/ma-SVP (PCM, toluene) and only change the PCM radius of bromine.

By doing this, the TS optimization was successful without oscillating behavior. Do you think that this could actually be a generally better way to calculate bromine-containing molecules, even when using functionals and basis sets that are different from the original SMD18 paper?

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