[gmx-users] Positive Coul. recip. term

Dommert Florian dommert at icp.uni-stuttgart.de
Wed Feb 29 11:47:03 CET 2012


On Mon, 2012-02-27 at 11:05 -0700, Denny Frost wrote:
> The ionic liquid is bistriflate N-methyl-N-propyl pyrrolidinium and
> the force field is from Lopes (CLaP).  I tried deleting all of the
> cation dihedrals from the itp file and found that the run did not
> crash, although it still had a positive coul recip term.  Upon
> examination of the cation dihedrals I noticed that there was a typo in
> which a set of unbonded carbons were put together in a dihedral term.
>  Perhaps this is what made the previous runs crash.  
> Even with this correction, the coul. recip. term is still positive.  I
> have tried smaller time steps and changing ewald_tol to 1e-3, but
> these have not resolved this issue.  How can I calculate the error in
> the electrostatic force?
> Denny
> 

The error of PME can be estimated a priori with the tool g_pme_error. I
would suggest to tune it to a bound below 1e-3. 

I took a look at the force field parameters for the pyrrolidinium, which
is published by Lopes in 2006, and I assume you use this parameters, are
you ? 

I do not understand Table I in this paper. The dihedral parameters are
just given for V_2 and V_4, and for a certain dihedral they are even set
to zero. If you use this force field, how are the other parameters
obtained ? Are they zero or do they correspond to the OPLS values given
in the reference cited on the top of the table ? 


/Flo

> On Sat, Feb 25, 2012 at 4:43 AM, Dommert Florian
> <dommert at icp.uni-stuttgart.de> wrote:
>         On Fri, 2012-02-24 at 11:03 -0700, Denny Frost wrote:
>         > Thank you both for your replies.  I currently have another
>         ionic
>         > liquid running just fine on the same gromacs build (compiled
>         the tpr
>         > file yesterday), so I am reluctant to conclude that the
>         problem is
>         > with the linking.  Please let me know if you disagree.
>         > The force field I am using was published in 2004 and has
>         been
>         > validated by another group.  I have double and triple
>         checked my itp
>         > files to make sure they match the force field, but it's
>         possible there
>         > are still some errors there.
>         
>         
>         Is it the force field of Lopes (CLaP) et al. or Liu et al.
>         (LHW) and who
>         validated it, I am just curious, and what is the ionic
>         liquid ?
>         
>         Though you are constraining the hbonds, I would be cautious
>         with the
>         time step of 2fs, because it might be, that the eigenfrequency
>         of the
>         anionic bonds requires a shorter time step, but this should
>         not be the
>         problem of a positive Coulomb energy. Have you calculated the
>         error in
>         the electrostatic force ? I would suggest to tune it to a
>         limit of 1e-3,
>         perhaps this resolves the problem of the positive Coulomb
>         term.
>         
>         Perhaps some 1--4 and dihedral interactions are missing in the
>         itp file,
>         so assure if all of them are provided correctly.
>         
>         /Flo 
>         
>         > I agree that this is very strange and feel that there must
>         be
>         > something fundamentally wrong in the mdp file or deeper.  I
>         have
>         > included my mdp file below.
>         >
>         >
>         > title               =  PMP+TFN
>         > cpp                 =  /lib/cpp
>         > constraints         =  hbonds
>         > integrator          =  md
>         > dt                  =  0.002   ; ps !
>         > nsteps              =  10000000   ; total 20 ns
>         > nstcomm             =  10
>         > nstxout             =  50000
>         > nstvout             =  50000
>         > nstfout             =  0
>         > nstlog              =  5000
>         > nstenergy           =  5000
>         > nstxtcout           =  25000
>         > nstlist             =  10
>         > ns_type             =  grid
>         > pbc                 =  xyz
>         > coulombtype         =  PME
>         > vdwtype             =  Cut-off
>         > rlist               =  1.2
>         > rcoulomb            =  1.2
>         > rvdw                =  1.2
>         > fourierspacing      =  0.12
>         > pme_order           =  4
>         > ewald_rtol          =  1e-5
>         > ; Berendsen temperature coupling is on in two groups
>         > Tcoupl              =  v-rescale
>         > tc_grps             =  PMP   TFN
>         > tau_t               =  0.2  0.2
>         > ref_t               =  300  300
>         > nsttcouple          =  1
>         > ; Energy monitoring
>         > energygrps          =  PMP   TFN
>         > ; Isotropic pressure coupling is now on
>         > Pcoupl              =  berendsen
>         > pcoupltype          =  isotropic
>         > tau_p               =  2.0
>         > ref_p               =  1.0
>         > compressibility     =  4.5e-5
>         >
>         >
>         > ; Generate velocites is on at 300 K.
>         > gen_vel             =  yes
>         > gen_temp            =  300.0
>         > gen_seed            =  -1
>         >
>         >
>         >
>         > On Fri, Feb 24, 2012 at 12:17 AM, Dommert Florian
>         > <dommert at icp.uni-stuttgart.de> wrote:
>         >         On Thu, 2012-02-23 at 13:35 -0700, Denny Frost
>         wrote:
>         >         > Dear all,
>         >         > I am trying to equilibrate a solvent of pure ionic
>         liquid.
>         >          The system
>         >         > keeps exploding (after 2-5 ns) and I am not sure
>         why, though
>         >         I believe
>         >         > coulombic interactions are to blame.  This is
>         because the
>         >         Coul-SR term
>         >         > is negative, but the Coul. recip term is very
>         positive
>         >         throughout the
>         >         > entire run (giving the entire system a positive
>         potential
>         >         energy).  I
>         >         > think this means that the short-range
>         electrostatics are
>         >         okay, but the
>         >         > long range electrostatics (calculated with PME)
>         are not.
>         >          Does anybody
>         >         > have any suggestions as to why this would happen?
>          I have
>         >         used the
>         >         > exact same PME input parameters for another ionic
>         liquid
>         >         that works
>         >         > just fine.  They are listed below.
>         >         >
>         >         >
>         >         > rcoulomb = 1.2
>         >         > fourierspacing = 0.12
>         >         > pme_order = 4
>         >         > ewald_rtol = 1e-5
>         >         >
>         >
>         >
>         >         Depends on the force field you are using. Perhaps it
>         ist not
>         >         validated
>         >         for the ionic liquid you want to study. It is
>         especially
>         >         strange, that
>         >         it takes so long for your system to blow up.
>         >
>         >         Moreoever I would try to optimize the PME settings
>         with the
>         >         tools,
>         >         g_tune_pme and g_pme_error, which give you
>         performance and
>         >         accuracy of
>         >         the parameters, respectively.
>         >
>         >         So perhaps with some more information I can provide
>         more help.
>         >
>         >         /Flo
>         >
>         >         >
>         >         > Thanks!
>         >         > Denzil Frost
>         >         > --
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>         >         --
>         >         Florian Dommert
>         >         Dipl. - Phys.
>         >
>         >         Institute for Computational Physics
>         >         University Stuttgart
>         >
>         >         Pfaffenwaldring 27
>         >         70569 Stuttgart
>         >
>         >         EMail: dommert at icp.uni-stuttgart.de
>         >         Homepage:
>         http://www.icp.uni-stuttgart.de/~icp/Florian_Dommert
>         >
>         >         Tel.: +49 - (0)711 - 68563613
>         >         Fax.: +49 - (0)711 - 68563658
>         >
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>         
>         --
>         Florian Dommert
>         Dipl. - Phys.
>         
>         Institute for Computational Physics
>         University Stuttgart
>         
>         Pfaffenwaldring 27
>         70569 Stuttgart
>         
>         EMail: dommert at icp.uni-stuttgart.de
>         Homepage: http://www.icp.uni-stuttgart.de/~icp/Florian_Dommert
>         
>         Tel.: +49 - (0)711 - 68563613
>         Fax.: +49 - (0)711 - 68563658
>         
>         
>         --
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-- 
Florian Dommert
Dipl. - Phys.

Institute for Computational Physics
University Stuttgart

Pfaffenwaldring 27
70569 Stuttgart

EMail: dommert at icp.uni-stuttgart.de
Homepage: http://www.icp.uni-stuttgart.de/~icp/Florian_Dommert

Tel.: +49 - (0)711 - 68563613
Fax.: +49 - (0)711 - 68563658
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