[gmx-developers] high-precision TIP3P parameters?

Igor Leontyev ileontyev at ucdavis.edu
Mon May 29 06:02:49 CEST 2017


 > True, but also makes GROMACS different from past versions of itself,
 > which
 > also would worry people doing such a comparison when e.g.contemplating
 > upgrading their version.

Changing Amber parameters will not affect other force fields, with which 
the comparison with older gmx versions will remain exact.

 > We're all for doing things correctly, but that
 > should mean everybody actually implementing the published/accepted
 > value,
 > not agreeing with each other on how to be different.It sounds like
 > we're happy enough to change the values in GROMACS to
 > match
 > the paper - can people please raise the issue/question with others who
 > distribute parameter sets?
 >
 > Mark

For Amber FF there is an issue with what is PUBLISHED and what is 
ACCEPTED. If I remember, parameters in Amber TIP3P model (given by 
tleap) are bit different from those in the original Jorgensen TIP3P 
paper. BUT ...
The entire Amber FF was developed validating and if necessary adjusting 
other species parameters for matching experiment in simulations with 
that Amber TIP3P water. So if we want to remain within the scope of 
Amber Force Field standard, as opposite to introducing NEW 
"Amber-in-gromacs" standard, we have to use TIP3P parameters from Amber 
tleap (despite they are different from both the Jorgensen paper and 
current gromacs).

Igor


On 5/26/2017 5:10 PM, Igor Leontyev wrote:
> Hi,
> It is unlikely that inaccuracy in 4th digit of the parameters could
> introduce significant error in simulation results.
>
> However, for the energy comparison and debugging which is often made by
> curious people (including myself) when switching between Amber and
> Gromacs codes the inaccuracy is really bothering. Accepting suggested
> correction will match Amber and Gromacs code energies and make the
> comparison perfect (possibly for the cost of one time issue with
> regression test).
>
> Igor
>
>>
>> Hi,
>>
>> These difference are irrelevant for any practical purposes, since the
>> model (and sampling) is not by far that accurate. But it would still be
>> nice to have all decimals that we have in files correct.
>> Is this somehow related to the differences in the kcal/mol to kJ/mol
>> conversion in different packages and/or at different times?
>>
>> Cheers,
>>
>> Berk
>>
>> On 24/05/17 21:18 , Igor Leontyev wrote:
>>> Hi all. The issue was discussed in past but nothing was corrected
>>> since then.
>>>
>>> https://mailman-1.sys.kth.se/pipermail/gromacs.org_gmx-developers/2011-April/005178.html
>>>
>>>
>>>
>>> To make gromacs TIP3P energies matching Amber code energies:
>>>> Suggested correction in amberXX.ff/ffnonbonded.itp:
>>>> ;OW           8      16.00    0.0000  A   3.15061e-01 6.36386e-01
>>>> OW           8      16.00    0.0000  A   3.15076e-01 6.35968e-01
>>>
>>> Igor
>>>
>>>>  So, going back to the original TIP3P paper, the parameters are listed
>>> as A and C parameters (in the formula a/r^12 ? b/r^6).
>>>>
>>>> The parameters listed there are A = 582000 A^12 kcal/mol and C = 595
>>>> A^6 kcal/mol.
>>>>
>>>> Converting to sigma/epsilon form, this gives:
>>>> Sigma = 0.31506561105 nm
>>>> Epsilon = 0.6362717354 kJ/mol
>>>>
>>>> This compares with the values in the most of the distributed ITP
>>>> files of
>>>>
>>>> Sigma = 0.315061 nm (a difference of 4.6 x 10^-6 nm, or a relative
>>>> difference of  of 1.4 x 10^-5)
>>>> Epsilon =  0.636386 kJ/mol (a difference of 1.1 x 10^4 kJ/mol, or a
>>>> relative difference of 1.8 x 10^-4)
>>>>                         (note the GROMACS one is also 0.152100
>>>> kcal/mol)
>>>> I don?t know how much of a difference this would make (likely a
>>>> difference of the scale of).
>>>>
>>>> Now, that?s in the original paper.  What values are ACTUALLY
>>>> specified by other codes?
>>>>
>>>> For AMBER, (as produced by tleap), it outputs.
>>>>
>>>> A = 581935.564     A^12 kcal/mol
>>>> C = 594.825035      A^6 kcal/mol
>>>>
>>>> Which leads to:
>>>>
>>>> Sigma = 0.315075 (a difference of 3.0 x 10^-5 nm, or a relative
>>>> difference of 3.0 x 10^-5)
>>>> Epsilon = 0.635968 kJ/mol  (a difference of 9.4 x 10^4 kJ/mol or a
>>>> relative difference of 4.7 x 10^-4)
>>>>                          (which is also 0.152000 kcal/mol)
>>>>
>>>> So ? I don?t know.  Nobody seems to be getting it _exactly_ right,
>>>> and it?s also not so clear how much of a difference it makes.   One
>>>> can estimate that enthalpies would have a relative error of around
>>>> 10^-4, and relative errors in the density of 3*dsigma = 10^-4 to 10^-5.
>>>>
>>>> So I don?t know that there is anything actionable to take.  Just
>>>> thought it was interesting to bring out.  Something to ponder for now.
>>>
>
>>
>> I?d say ?probably? irrelevant for practical purposes.  It wouldn?t
>> take too much simulation time to determine the density sensitively
>> enough to tell the difference.  But, pretty much irrelevant.
>>
>> ?     Is this somehow related to the differences in the kcal/mol to
>> kJ/mol
>> ?     conversion in different packages and/or at different times?
>>
>> I think that it?s due to differences in rounding from the original A
>> and C values vs. rounding from conversion of them to epsilon and sigma
>> values. The epsilons in AMBER and GROMACS are clearly equal to using
>> either 0.152100 or 0.15200 kcal/mol as the value (the parameters in
>> the original paper correspond to 0.151207).
>>
>> I think there might have been a kJ/kcal issue at some point, but those
>> were fixed a decade or so ago (I seem to recall that popping up when I
>> was a graduate student, but not since then).
>>
>> ?     These difference are irrelevant for any practical purposes,
>> since the
>> ?     model (and sampling) is not by far that accurate. But it would
>> still be
>> ?     nice to have all decimals that we have in files correct.
>>
>> At this stage, it probably involves getting some general set everyone
>> together and deciding in what the ?right? values are. I could
>> potentially do that . . . but as Berk points out, not that big a
>> deal.  Unless one is trying to match energy snapshots, and getting
>> frustrated.
>>
>> For what it?s worth, the Desmond viparr utility uses for TIP3P:
>> {"sigma": 3.15061, "epsilon": 0.1521}.  Both match GROMACS .itp
>> libraries, but not tleap or the original paper.
>>
>> Best,
>> ~~~~~~~~~~~~~~~~
>> Michael Shirts
>> Associate Professor
>> michael.shirts at colorado.edu
>> http://www.colorado.edu/lab/shirtsgroup/
>> Phone: (303) 735-7860
>> Office: JSCBB C123
>> Department of Chemical and Biological Engineering
>> University of Colorado Boulder
>>
>> On 5/25/17, 1:51 PM,
>> "gromacs.org_gmx-developers-bounces at maillist.sys.kth.se on behalf of
>> Berk Hess" <gromacs.org_gmx-developers-bounces at maillist.sys.kth.se on
>> behalf of hess at kth.se> wrote:
>>
>>     Hi,
>>
>>     These difference are irrelevant for any practical purposes, since the
>>     model (and sampling) is not by far that accurate. But it would
>> still be
>>     nice to have all decimals that we have in files correct.
>> Is this somehow related to the differences in the kcal/mol to kJ/mol
>>     conversion in different packages and/or at different times?
>>
>>     Cheers,
>>
>>     Berk
>>
>>     On 24/05/17 21:18 , Igor Leontyev wrote:
>>     > Hi all. The issue was discussed in past but nothing was corrected
>>     > since then.
>>     >
>>     >
>> https://mailman-1.sys.kth.se/pipermail/gromacs.org_gmx-developers/2011-April/005178.html
>>
>>     >
>>     >
>>     > To make gromacs TIP3P energies matching Amber code energies:
>>     > > Suggested correction in amberXX.ff/ffnonbonded.itp:
>>     > > ;OW           8      16.00    0.0000  A   3.15061e-01 6.36386e-01
>>     > > OW           8      16.00    0.0000  A   3.15076e-01 6.35968e-01
>>     >
>>     > Igor
>>     >
>>     >>  So, going back to the original TIP3P paper, the parameters are
>> listed
>>     > as A and C parameters (in the formula a/r^12 ? b/r^6).
>>     >>
>>     >> The parameters listed there are A = 582000 A^12 kcal/mol and C
>> = 595
>>     >> A^6 kcal/mol.
>>     >>
>>     >> Converting to sigma/epsilon form, this gives:
>>     >> Sigma = 0.31506561105 nm
>>     >> Epsilon = 0.6362717354 kJ/mol
>>     >>
>>     >> This compares with the values in the most of the distributed ITP
>>     >> files of
>>     >>
>>     >> Sigma = 0.315061 nm (a difference of 4.6 x 10^-6 nm, or a relative
>>     >> difference of  of 1.4 x 10^-5)
>>     >> Epsilon =  0.636386 kJ/mol (a difference of 1.1 x 10^4 kJ/mol,
>> or a
>>     >> relative difference of 1.8 x 10^-4)
>>     >>                         (note the GROMACS one is also 0.152100
>> kcal/mol)
>>     >> I don?t know how much of a difference this would make (likely a
>>     >> difference of the scale of).
>>     >>
>>     >> Now, that?s in the original paper.  What values are ACTUALLY
>>     >> specified by other codes?
>>     >>
>>     >> For AMBER, (as produced by tleap), it outputs.
>>     >>
>>     >> A = 581935.564     A^12 kcal/mol
>>     >> C = 594.825035      A^6 kcal/mol
>>     >>
>>     >> Which leads to:
>>     >>
>>     >> Sigma = 0.315075 (a difference of 3.0 x 10^-5 nm, or a relative
>>     >> difference of 3.0 x 10^-5)
>>     >> Epsilon = 0.635968 kJ/mol  (a difference of 9.4 x 10^4 kJ/mol or a
>>     >> relative difference of 4.7 x 10^-4)
>>     >>                          (which is also 0.152000 kcal/mol)
>>     >>
>>     >> So ? I don?t know.  Nobody seems to be getting it _exactly_ right,
>>     >> and it?s also not so clear how much of a difference it makes.
>> One
>>     >> can estimate that enthalpies would have a relative error of around
>>     >> 10^-4, and relative errors in the density of 3*dsigma = 10^-4
>> to 10^-5.
>>     >>
>>     >> So I don?t know that there is anything actionable to take.  Just
>>     >> thought it was interesting to bring out.  Something to ponder
>> for now.


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