R_Recombination rules too fast, again

[rwest]

trafficstars

• Issue #353 highlighted that some R_Recombination reactions were much too fast, using the auto-generated tree.
• PR #355 attempted to patch it by replacing an auto-generated Blowers Masel rate which had A=(1.55409e+91,'m^3/(mol*s)'), n=-24.7026, with a more reasonable collision limit.
• PR #369 regenerated the R Recombination tree, which hopefully addressed things somewhat.

With the new tree, I am generating reactions that show up in a collision limit violators notebook.

For example: HNOH(94) + CH2OH(45) <=> ONCO(964) Arrhenius(A=(6.89518e+79,'cm^3/(mol*s)'), n=-21.017, Ea=(0,'kcal/mol'), T0=(1,'K')) BM rule fitted to 2 training reactions at node Root_N-1R->H_1CNOS->N_Ext-2R-R_3R!H-u0_2R->C Total Standard Deviation in ln(k): 11.5401827615 Exact match found for rate rule [Root_N-1R->H_1CNOS->N_Ext-2R-R_3R!H-u0_2R->C] Euclidian distance = 0 family: R_Recombination Direction: forward Violation factor: 2e+10 Violation condition: 423 K, 1.0 bar

There are several others, all exceeding the collision limit by a factor of more than 10^10. And they all hit the same node, and have an Arrhenius A=(6.89518e+79,'cm^3/(mol*s)'), n=-21.017 rule fitted to 2 training reactions.

Once again, it has a huge A and big negative n. Same problem as before. Probably worked in a narrow range where fitted, but being extrapolated to a different T.

I wonder if the fitting might benefit from some form of regularization, to penalize huge n parameters and make things extrapolate better?

I wonder if the collision limit violation test could be automated for all these auto-generated rules? So someone could at least look into fixing them before they show up in models.

[mjohnson541]

This one seems to be in violation even at higher temperatures T = 1000 K. Regularization is probably a bit dangerous in these situations with so few parameters. Enabling estimation to move up the tree when uncertainty is high may help. I could add a processing step analyzing generated rules for potential collision limit violations and refitting, it's tricky to do this generally, but we could probably detect most things. I'm not exactly sure how this one was possible. I'll try to take a look at this later this week.