2024-04-24 FF Fitting Meeting

Participants

  • @Willa Wang

  • @Brent Westbrook

  • @Alexandra McIsaac

  • @David Mobley

  • @Michael Gilson

  • @Pavan Behara

  • @Christopher Bayly

  • @Matt Thompson

  • @Jeffrey Wagner

Goals

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Discussion topics

Item

Presenter

Notes

Item

Presenter

Notes

Polarizable water model update

Willa Wang

  • Slides/recording: https://us06web.zoom.us/rec/share/V3wQkC5HPMtIg5WlKRc8CsHcCtAxHJHNk6GPkkZEJk99kN9PlwgtZJUnIYVPCnoJ.GpD50IP6zSblzDGZ
    Passcode: H4Eba.x4

  • Previously, temperature-dependent properties weren’t being fitted. Now, faster process can fit across multiple temperatures

  • Result is good compared to TIP3P, but not as good as OPC3

  • MG: (slide 7/8) You said you thought fluctuations might be due to polarizable water model requiring longer run, but TIP3P also has those fluctuations

    • WW: Maybe all of them need to be run longer, or maybe it’s not an issue with polarization

  • MG: (Slide 8) Heat of vaporization--brown curve is TIP3P, we’re very close

  • MG (slide 8) Looks competitively accurate vs TIP3P, would you agree?

    • WW: yes, though not as good as OPC3

  • WW: OPC3 has good dielectric, not sure why

    • MG: 1/dielectric is what matters

    • MG: OPC3 has correction to heat of vaporization so that comparison isn’t necessarily comparable

    • [a bit more discussion around 14 min in the recording]

  • WW: angle parameter is 111.8 deg, vs expt 104.52. is that a problem?

    • JW: If you have workflow set up, you could try re-doing the fit but keeping the geometry at the expt

      • WW: Started with that, but didn’t give good results, high objective function.

      • WW: Only TIP3P keeps experimental geometry, and it’s the worst model. Historically, usually need to change the geometry

    • CB: Is experimental geometry for gas phase?

      • WW: Yes

      • CB: Do we know it for liquid? OPC3 also has larger angle, maybe the angle is larger in liquid

      • WW: Will look into it

  • CB: Did you compare to polarizable water model? I joined late

    • WW: no, not yet

    • CB: Wondering if differences from expt could be due to not including induced polarization

    • WW: iAMOEBA reproduced almost exact T-dependent density. Direct polarizability only, but has multipole expansion

  • MG: Slope of density vs T graph is same as coeff of thermal expansion being too big. Could consider increasing weight on coeff of thermal expansion at 300K. Not sure why it would be better than what you did, but could be

    • WW: Yeah, could try that if we want further improvement

  • WW: If angle is ok, I want to stop with the optimization, I think it’s good enough

  • JW: When you tried using experimental geometry, optimization objective increased?

    • WW: Density and dielectric constant were way too high, that’s why the objective was bad, started too high and any change in parameters made it worse

  • CB: Trying to brainstorm why qualitative difference from expt? Can you compare with iAMOEBA?

    • WW: doesn’t work with OpenMM, so would be a lot of work

    • CB: Does iAMOEBA have large angle also? Would be good to identify which differences are due to polarizability

    • WW: Sharing iAMOEBA direct paper, almost perfectly agrees with expt. AMOEBA mutual is close but not perfect, AMOEBA direct looks similar to my model

    • MG: Doesn’t look like a direct mapping from polarization type to result, other factors are affecting it

    • MG: Would be good to know difference between amoeba direct and iamoeba direct

    • WW: I think iAMOEBA is flexible water

    • WW: iAMOEBA has smaller water angle, closer to expt

    • CB: Charge is different also for O

    • MG: iAMOEBA has no LJ on H, slightly larger O

    • WW: We don’t have LJ on H, tried but didn’t help

    • MG: What’s our O sigma?

    • WW: 3.189 A, smaller than iAMOEBA

    • WW: iAMOEBA is 14-7, hard to compare

    • CB: Wonder if you’re in a local minimum in parameter space

    • WW: Don’t think so, could be another minimum that is less physically meaningful. E.g. could make sigma very small to get better heat of vaporization, but wouldn’t be physically reasonable. But also don’t have any data showing it’s a global minimum, how could I show that?

    • CB: Start with iAMOEBA parameters, hold frozen except sigma, re-tune sigma (to adjust for functional form diff), then compare to that model. Then, try another optimization with that starting point, to see where it goes

    • WW: iAMOEBA is trained on intense training set, fits to a bunch of different properties and data, so would have very different objective function

    • CB: Changing the starting condition (especially to one that might be close to a minimum, given its performance) could just help you locate a second minimum

  • WW: Given this discussion, do we think the model needs to be tuned more?

  • MG: A few of the graphs on slide 8 are noisy, need longer runs…when you do FB optimization, is the noisiness reflected as errors in the gradient? Could lead to trouble hitting minimum

    • WW: Good point, think that’s possible

    • MG: How many temperatures are you using for training?

    • WW: 8

    • MG: Given that thermal expansion, which is noisy, also feeds into density--might make sense to do longer runs for ~3 temperatures to improve

    • WW: Can try that

    • CB: Could experiment by training just on quick properties and see if that fixes it

  • PB (chat): Lee Ping talks about gradients here https://pubs.acs.org/doi/10.1021/acs.jpcb.9b05455

    • PB: Lee-Ping did 20 ns simulation with TIP3P and didn’t see that noisiness

    • WW: I save my trajectory every 100 ps, maybe that contributes to noise. Is there a best practice for how often to save?

    • PB: Not sure

    • MG: They have error bars, maybe did multiple runs and averaged

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Action items

Decisions

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