ReactionMechanismGenerator / ReactionMechanismGenerator/RMG-database

R_Recombination rules too fast, again

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#378 1 comment 0 reactions 1 assignee View on GitHub

@mjohnson541 is already working on this.

Since Jan 5, 2020.

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Description

  • 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:
image
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.

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