[gmx-users] Positive Coul. recip. term

Dommert Florian dommert at icp.uni-stuttgart.de
Wed Feb 29 19:49:29 CET 2012


On Wed, 2012-02-29 at 11:12 -0700, Denny Frost wrote:
> The parameters I used are from the following reference:
> 
> Canongia Lopes and Padua, J. Phys. Chem. B 2004, 108, 16893
> 
> 
> This paper gives the bonded parameters of the anion and the non-bonded
> parameters of both ions.  The bonded parameters of the cation were
> obtained (as indicated in the reference above) from the OPLS force
> field. (Rizzo and Jorgensen, JACS 1999, 121, 4827).  

> Fixing the dihedral error I mentioned in my last email has kept the
> system from crashing.  The coul. recip term is still positive,
> however.  
> 
> 
> g_pme_error gave a Direct space error estimate of 9.8e-3 kJ/mol*nm and
> a Reciprocal space error estimate of 3.3 kJ/mol*nm.
> 

Look there is a big discrepancy between the real and reciprocal space
error, such that your overall force has an error in the order of 10^0,
but if you distribute the error over the real and reciprocal part by a
change of ewald_rtol, you can descrease this error. g_pme_error with the
flag -tune does this for you. Accordingly, by a decrease of the fourier
spacing, the error can be further decreased to the desired accuracy.
Hence you can check if the positive Coulomb term is an artefact of low
accuracy.

/Flo




> On Wed, Feb 29, 2012 at 3:47 AM, Dommert Florian
> <dommert at icp.uni-stuttgart.de> wrote:
>         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
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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
>         >
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>         >
>         >
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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
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>         
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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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