[gmx-users] Simulating PMMA

Karel de Vries kjcdevries at gmail.com
Fri Sep 30 09:35:49 CEST 2016


Hi again,

I think the problem is in the force field description that I put in the
aminoacids.rtp file. Like I said, I just got the output from Justin's
TopolGen (V1.1) script. Upon comparison of the opls_xxx choices to the
comments in the atomtypes.atp file, a few strange assignments turn up. For
example, the Os are taken to be from the C=O in an amide. However, there is
no nitrogen in PMMA at all. There is a C=O in PMMA, but it's an ester
group. There are a few more doubtful choices, e.g. a C bound to four other
Cs is assigned the "alkane CH3" atom.

I have two questions.
One concerns the TopolGen script: are these seemingly incorrect assignments
intentional? Or is this just a limitation in the script? There is another
TopolGen topology for PMMA online, at
http://gromacs-oplsaa-topologies.wikia.com/wiki/PMMA_3-mer, which has
slightly different but similarly doubtful assignments.

The second is about the opls-aa force field. Is there any other
documentation on which assignments to make than just the comments in the
atomtypes.atp file?


Regarding Chaofu Wu's reply to my original email; thank you very much for
your comments. I accidentally sent a template file, not one used for an
actual run. I run gromacs with lower nst* values; when I need statistics I
make sure there are about 1000 frames in the energy file. Values I adjust
from the parameters I sent are nsteps, nst*, ref_t, ref_p, and for the
initial run also gen_vel / gen_temp. I'm sorry for the confusion.

Karel de Vries


On Wed, Sep 28, 2016 at 11:43 AM, Karel de Vries <kjcdevries at gmail.com>
wrote:

> Hello all,
>
> I'm trying to simulate bulk PMMA, poly(methyl methacrylate) in Gromacs.
> I'm using the opls-aa force field. I added a PMMA unit cell to the
> aminoacids.rtp file (listing below). I'm running a simulation with 30
> molecules of 50 unit cells each. I start by putting straight strands into
> the box with gmx insert-molecules.
>
> I think that my input parameters are incorrect. My first reason for
> thinking this is that it is very difficult to equilibrate this system: it
> takes a lot of computation time to get the internal pressure to equal the
> external one during NPT even at high temperatures. The second reason is
> that I find unrealistic values for the glass transition temperature and
> density of PMMA at room temperature.
>
> I have tried several combinations of NVT and NPT simulations at different
> temperatures to get the system to equilibrate. The most successful one is
> as follows. I start with an NPT simulation at 1000 bar of isotropic
> pressure at 900 K using Berendsen barostat with tau_p=5 and compressibility
> 4.5e-5. Then I slowly decreased the pressure to 1 bar in 8 steps of 10 ns
> each. Finally I ran a 40 ns NPT equilibration step at 1 bar at the end. The
> average pressure tensor over this 40 ns run is as follows:
>    Pressure (bar)
>     9.67017e-01   -4.24140e-01   -1.51426e+00
>    -4.24137e-01   -2.97605e+00   -3.38247e+00
>    -1.51425e+00   -3.38246e+00    2.07151e+00
> I'm not sure how good this is, but it's much better than anything else
> I've done.
>
> I then cool down from 900K to 550K in steps of 50K, 5 ns per simulation. I
> do not expect the average cooling rate (0.01 K/ps) to be unrealistically
> fast: 550K is well above the glass transition temperature of real PMMA and
> I sometimes see people in literature use similar rates during annealing in
> other polymers. I then cool down from 550K to 300K in steps of 10K, 5 ns
> per simulation. The average pressure tensor contains values that keep
> getting further away from zero. Moreover, I find a glass transition
> temperature of around 470K, while for real PMMA it should be around 400K.
> The final density is 1.01 g/cm3, while it should be around 1.18 g/cm3.
>
> I'm starting to think there is something wrong with my parameters here,
> either in the mdp file or in the force field parameters. Has anybody here
> got any experience with PMMA and can they tell me what I'm doing wrong?
>
> Thanks a lot in advance.
> Karel de Vries
>
>
>
>
>
> This is what I added to the .rtp file in the force field. I have similar
> definitions for the end chains, which have a H connected to C1 and C2,
> respectively. This was based on output by Justin Lemkul's TopolGen script,
> except I took the charges from an external source (don't remember where I
> found them, unfortunately).
> [ atoms ]
>      C1    opls_135   -0.376     1
>      C2    opls_135    0.009     1
>      H3    opls_140    0.212     1
>      H4    opls_140    0.155     1
>      C5    opls_145    0.650     2
>      C6    opls_135   -0.288     3
>      H7    opls_140    0.096     3
>      H8    opls_140    0.096     3
>      H9    opls_140    0.096     3
>     O10    opls_236   -0.286     2
>     C11    opls_166   -0.161     2
>     O12    opls_236   -0.563     2
>     H13    opls_140    0.120     2
>     H14    opls_140    0.120     2
>     H15    opls_140    0.120     2
>
> [ bonds ]
>     C1    C2
>     C1    H3
>     C1    H4
>    C11   H13
>    C11   H14
>    C11   H15
>    C11   O10
>     C6    H7
>     C6    H8
>     C6    H9
>     C2    C5
>     C2    C6
>     C5   O10
>     C5   O12
>     C2   +C1
>
>
>
>
> These are typical parameters I've got in the mdp file:
> integrator               = md
> tinit                    = 0
> dt                       = 0.001
> nsteps                   = 1000000 ; 1 ns
>
> emtol                    = 100
> emstep                   = 0.001
> niter                    = 20
> fcstep                   = 0
> nstcgsteep               = 1000
> nbfgscorr                = 10
>
> cutoff-scheme            = Verlet
> nstxout                  = 1000000
> nstvout                  = 1000000
> nstfout                  = 1000000
> nstlog                   = 2000000
> nstenergy                = 10000
> nstxout-compressed       = 10000
> compressed-x-precision   = 1000
> rcoulomb                 = 1.00
> nstlist                  = 45
> ns_type                  = grid
> pbc                      = xyz
> rlist                    = 1.00
> vdw-type                 = cut-off
> vdw-modifier             = Potential-switch
> rvdw-switch              = 0.8
> rvdw                     = 1.00
>
> Tcoupl                   = v-rescale
> tc-grps                  = System
> tau_t                    = 0.2
> ref_t                    = 900
> Pcoupl                   = berendsen
> Pcoupltype               = isotropic
> tau_p                    = 5.0
> compressibility          = 4.5e-5
> ref_p                    = 1.0
>
> gen_vel                  = no
> gen_temp                 = 900
> gen_seed                 = 1000
>
> DispCorr                 = EnerPres
>
>
>
>


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