[gmx-users] Fwd: PE compressing - for reference only

Vitaly Chaban vvchaban at gmail.com
Sat Jul 24 15:37:31 CEST 2010


Dear Moeed:

Please find attached the simulation results as well as the input files
for your PE system. I started the simulation from your 8PE
configuration and compressed it to the density of ~890 kg/m3. It is
rather good since ranges between the experimental values -
http://en.wikipedia.org/wiki/Polyethylene .The system is also in
equilibrium (please see the attached plot). I think this is what you
need to start productive runs.

You might also want to adjust charges but this is up to you. I suppose
the average density can become slightly larger if you increase the
system size because now the system is very modest as compared to the
size of one PE particle.


> 1- In general in most of the NPT runs I am not reaching the reference
> pressure ( 50 ,30 ..bar). I get very low values around zero or 1.

I've just performed the simulation at 30 bar during 2 000 ps and got

Energy                      Average       RMSD     Fluct.      Drift  Tot-Drift
-------------------------------------------------------------------------------
Pressure (bar)              30.1703    1373.51    1368.76  -0.790566
-395.285

Thus, no problems with NPT... I also think you do not NVT at all in this study.

> 2-About bond constraints: Actually, in literature I see it is common to fix
> the bond distance. Also in one of the GROMACS tutorials I have seen the
> reasoning that" since bond vibrations are of quantum nature they can not be
> treated classically". The reason you mentioned that I am noy using a good
> force filed is because of using bond constraints or ...? Do I need to remove
> constraints?


The fixation of the interatomic distances is not so common. The
general rule is not to use constraints&restraints if you can avoid
their usage. In my opinion, your system need not constaints. I did not
just used them on your system (see MDP attached).

The force field looked suspicious since you got LINCS warning. With a
correct setup and interaction parameters, no warnings should be
present.


> 3- I have another inquiry about treating electrostatics contribution in my
> system. My systems as you have noticed involves only C and H. Later I will
> have to solvate this PE chain in HExane which is again apolar (only partial
> charges). It is not still clear to me whether I need to include
> electrostatic energy terms or I need to consider only vdw for calculating
> interaction energies

>From the scientific point of view, I'd suggest to run both cases and
then conclude about the role of electrostatics in your particular
polymer system. Generally, you need electrostatics in order to
represent all the non-bonded interactions correctly, even if the
partial charges are negligible. I do not like SHIFT for
electrostatics, please use PME as I recently did with your system
(attached MDP).



> 4-the value of compressibility I am using in mdp file is 4.5e-5 which is for
> water. I have not found this valued for my polymer yet.

This value is not critical. Usually, the guys use the same value
(almost) for all systems. Read about Parrinello-Rahman pressure
coupling for the more comprehensive insight on how to get
compressibility.


Also, please pay attention to the modified MDP file. These parameters
look better for your particular system.

For the productive runs, I'd suggest you to enlarge the simulation
box, so it is significantly longer or at least not shorter than the PE
chain. I also suppose it will give some increase of density since the
voids due to polymer complicated structure will become smaller as
compared to the overall box volume.

Good luck!

Dr. Vitaly Chaban




On Sat, Jul 24, 2010 at 5:42 AM, Moeed <lecielll at googlemail.com> wrote:
> Dear Dr. Chaban,
>
> First of all, I thank you for you kind attention. I am a PhD student at
> McGill and my topic revolves around computational thermodynamics of polymer
> solutions. I appreciate any comment or suggestion...
>
> ( I am focusing on calculating interaction energies between PE HExane and
> using these values in thermodynamic model. At the moment I have only PE and
> would like to study a pure polymer system. I would like also to look into
> free energy of solvation, rms, Rg, .. and very importantly surface tension
> calculations)
>
> I noticed that in either NPT or NVT trials for a long chain (PE60.gro)
> equilibrium state corresponds to more extended conformations. I noticed the
> only way to approach the volume I am after is forget the equilibrium state
> (as if simulation is long chain tends to extend) and I looked for the
> globule-like structure so the volume it occupies is minimal. For instance I
> did a NPT for 100ps and viewing the trajectory I noticed at 30 ps molecule
> has the convoluted structure so in the next trial I picked simul. time of 30
> ps to capture the structure I want (PE60-P150-30ps, pressure 150) , then
> used editconf to reduce the size (editconf888 8*8*8nm) energy minimized the
> structure and performed the next NPT with this initial structure. Doing so,
> I could approach the box size of 2.26 nm (desired size is 1.8nm).
>
> File names I have picked make it easy to follow the steps (especially if you
> view the files using "List option" or "details option" in your directory) I
> have taken from the initial PE chain (PE60.gro)
>
> PE60-P150-30ps-editconf888-P50-100ps-NVT140ps-editconf444center_bfpr.gro
> this is still a single chain in box of size 4 4 4 and _b4pr indicates the
> last step has been EM.
>
> after this I did two more NPT runs:
>
> PE60-P150-30ps-editconf888-P50-100ps-NVT140ps-editconf444center_bfpr-NPT120-100ps-NPT50-100p.gro
>> this is renamed to PE60-box2.26
>
> and got box size of 2.26nm
>
> Since it was not possible to compress the system further I replicated this
> molecule and energy minimized the replicated system to 8 chains
> (PE60-box2.26-nbox222). Energy minimization gives reasonable force but
> potential is about 3000. I dont know if this is reasonable for such a packed
> system (PE60-box2.26-nbox222_bfpr)
>
> Then employed NPT to compress again to a volume a bit smaller (3.34nm) than
> what I need and used editconf to attain the exact density I am after( which
> is size of 3.6nm after replicating 8 chains).  Below is the output file of
> EM of the replicated and compressed system:
>
> PE60-box2.26-nbox222_bfpr-P50-180ps-editconf3.6c_b4pr
>
> I am getting some LINC warnings but at the end force and potential energies
> seem to be OK. PLease let me know if anything is going wrong.
> :
> Steepest Descents:
>    Tolerance (Fmax)   =  1.00000e+03
>    Number of steps    =          400
> Step=    0, Dmax= 1.0e-02 nm, Epot=  1.32635e+08 Fmax= 2.29301e+10, atom=
> 1004
> Step=    1, Dmax= 1.0e-02 nm, Epot=  2.22267e+07 Fmax= 1.39980e+09, atom=
> 1766
> Step=    2, Dmax= 1.2e-02 nm, Epot=  8.21648e+06 Fmax= 2.00629e+08, atom=
> 968
> Step=    3, Dmax= 1.4e-02 nm, Epot=  1.67342e+06 Fmax= 2.38551e+07, atom=
> 968
> Step=    4, Dmax= 1.7e-02 nm, Epot=  4.59581e+05 Fmax= 3.28726e+06, atom=
> 121
> Step=    5, Dmax= 2.1e-02 nm, Epot=  1.51948e+05 Fmax= 4.17261e+05, atom=
> 1766
> Step=    6, Dmax= 2.5e-02 nm, Epot=  4.95460e+04 Fmax= 1.64740e+05, atom=
> 121
> Step=    7, Dmax= 3.0e-02 nm, Epot=  3.20548e+04 Fmax= 8.22273e+04, atom=
> 968
> Step=    8, Dmax= 3.6e-02 nm, Epot=  2.16962e+04 Fmax= 1.86463e+04, atom=
> 961
> Step=    9, Dmax= 4.3e-02 nm, Epot=  1.29190e+04 Fmax= 3.92749e+03, atom=
> 1766
>
> Step 10, time 0.02 (ps)  LINCS WARNING
> relative constraint deviation after LINCS:
> rms 0.001238, max 0.029289 (between atoms 113 and 115)
> bonds that rotated more than 30 degrees:
>  atom 1 atom 2  angle  previous, current, constraint length
>     113    114   33.6    0.1090   0.1103      0.1090
>    1765   1766   36.2    0.1090   0.1075      0.1090
> Step=   10, Dmax= 5.2e-02 nm, Epot=  8.04986e+03 Fmax= 3.49262e+04, atom=
> 826
>
> .
> .
> .Step 15, time 0.03 (ps)  LINCS WARNING
> relative constraint deviation after LINCS:
> rms 0.042648, max 1.350503 (between atoms 825 and 826)
> bonds that rotated more than 30 degrees:
>  atom 1 atom 2  angle  previous, current, constraint length
>     122    124   38.1    0.1093   0.1174      0.1090
>     122    123   34.0    0.1092   0.1165      0.1090
>     119    121   41.9    0.1092   0.1253      0.1090
>     119    120   44.7    0.1091   0.1219      0.1090
>     116    119   33.7    0.1541   0.1512      0.1529
>     113    116   40.5    0.1540   0.1564      0.1529
>     113    115   55.8    0.1095   0.1294      0.1090
>     113    114   49.4    0.1093   0.1263      0.1090
>     110    112   50.6    0.1094   0.1209      0.1090
>     110    111   53.4    0.1094   0.1218      0.1090
>     107    110   39.4    0.1534   0.1666      0.1529
>     107    108   35.4    0.1090   0.1178      0.1090
>     966    969   33.5    0.1534   0.1669      0.1529
>     966    968   44.8    0.1090   0.1172      0.1090
>     966    967   66.8    0.1091   0.1221      0.1090
>     963    965   38.5    0.1091   0.1181      0.1090
>     963    964   37.1    0.1091   0.1179      0.1090
>     831    834   31.6    0.1538   0.1448      0.1529
>     831    833   37.3    0.1099   0.0977      0.1090
>     828    831   55.2    0.1553   0.1785      0.1529
>     828    829   84.4    0.1113   0.1348      0.1090
>     825    828   56.5    0.1555   0.2214      0.1529
>     825    827   89.3    0.1102   0.1823      0.1090
>     825    826   89.2    0.1085   0.2562      0.1090
>     822    824   65.3    0.1092   0.1602      0.1090
>     822    823   51.3    0.1092   0.1482      0.1090
>     819    822   44.6    0.1534   0.1902      0.1529
>    1768   1770   45.1    0.1107   0.1528      0.1090
>    1768   1769   38.5    0.1101   0.1401      0.1090
>    1765   1768   55.7    0.1510   0.1687      0.1529
>    1765   1767   88.7    0.1145   0.1453      0.1090
>    1765   1766   90.4    0.1128   0.1744      0.1090
>    1762   1765   36.3    0.1601   0.1635      0.1529
>    1762   1764   42.7    0.1120   0.1163      0.1090
>    1762   1763   48.8    0.1101   0.1144      0.1090
>    1759   1760   38.9    0.1102   0.1097      0.1090
>    1591   1594   33.0    0.1533   0.1547      0.1529
>    1591   1593   36.9    0.1092   0.1158      0.1090
>    1591   1592   36.1    0.1091   0.1153      0.1090
>    1588   1590   38.0    0.1092   0.1140      0.1090
>    1588   1589   39.0    0.1092   0.1141      0.1090
>    1519   1522   34.1    0.1532   0.1709      0.1529
>    1519   1521   32.5    0.1091   0.1221      0.1090
>    1519   1520   35.2    0.1091   0.1232      0.1090
>    1516   1519   38.5    0.1533   0.1791      0.1529
>    1516   1518   51.8    0.1093   0.1334      0.1090
>    1516   1517   56.4    0.1094   0.1351      0.1090
>    1513   1515   58.5    0.1092   0.1557      0.1090
>    1513   1514   56.9    0.1092   0.1569      0.1090
>    1510   1513   60.5    0.1545   0.1522      0.1529
>    1510   1512   53.6    0.1103   0.1148      0.1090
>    1510   1511   41.7    0.1101   0.1016      0.1090
>    1507   1510   55.0    0.1545   0.1515      0.1529
>    1507   1509   58.9    0.1093   0.1563      0.1090
>    1507   1508   54.7    0.1092   0.1557      0.1090
>    1504   1506   45.3    0.1093   0.1293      0.1090
>    1504   1505   49.1    0.1094   0.1310      0.1090
>    1501   1504   38.9    0.1533   0.1749      0.1529
>    1818   1820   34.4    0.1091   0.1088      0.1090
>    2563   2565   39.8    0.1093   0.1167      0.1090
>    2563   2564   37.6    0.1093   0.1163      0.1090
>    2560   2562   42.1    0.1092   0.1220      0.1090
>    2560   2561   40.0    0.1092   0.1214      0.1090
>    2557   2560   35.8    0.1536   0.1535      0.1529
>    2554   2557   33.7    0.1537   0.1525      0.1529
>    2554   2556   37.1    0.1092   0.1219      0.1090
>    2554   2555   40.0    0.1092   0.1226      0.1090
>    2551   2553   36.5    0.1093   0.1167      0.1090
>    2551   2552   52.9    0.1092   0.1149      0.1090
> Wrote pdb files with previous and current coordinates
> Step=   15, Dmax= 1.3e-01 nm, Epot=  4.73137e+04 Fmax= 1.84271e+06, atom=
> 822
> Step 16, time 0.032 (ps)  LINCS WARNING
> relative constraint deviation after LINCS:
> rms 0.005654, max 0.128942 (between atoms 825 and 828)
> bonds that rotated more than 30 degrees:
>  atom 1 atom 2  angle  previous, current, constraint length
>     828    829   30.8    0.1113   0.1110      0.1090
>     825    828   31.7    0.1555   0.1726      0.1529
>     825    827   47.4    0.1102   0.1221      0.1090
>     825    826   76.4    0.1085   0.1166      0.1090
>     822    824   34.7    0.1092   0.1223      0.1090
>    1765   1767   37.2    0.1145   0.1126      0.1090
>    1765   1766   47.4    0.1128   0.1127      0.1090
> Step=   17, Dmax= 3.2e-02 nm, Epot=  3.09838e+03 Fmax= 2.83061e+03, atom=
> 1766
> Step=   18, Dmax= 3.9e-02 nm, Epot=  2.91458e+03 Fmax= 2.84186e+03, atom=
> 828
>
> Step 19, time 0.038 (ps)  LINCS WARNING
> relative constraint deviation after LINCS:
> rms 0.003357, max 0.050861 (between atoms 825 and 826)
> bonds that rotated more than 30 degrees:
>  atom 1 atom 2  angle  previous, current, constraint length
>     828    830   39.1    0.1095   0.1118      0.1090
>     825    826   39.2    0.1087   0.1145      0.1090
>    1516   1517   31.3    0.1094   0.1133      0.1090
> Step=   20, Dmax= 2.3e-02 nm, Epot=  2.38983e+03 Fmax= 1.82748e+03, atom=
> 1516
> Step=   22, Dmax= 1.4e-02 nm, Epot=  2.05520e+03 Fmax= 1.32025e+03, atom=
> 1510
> Step=   23, Dmax= 1.7e-02 nm, Epot=  2.00275e+03 Fmax= 2.13164e+03, atom=
> 1516
> Step=   24, Dmax= 2.0e-02 nm, Epot=  1.86550e+03 Fmax= 2.34225e+03, atom=
> 1510
> Step=   25, Dmax= 2.4e-02 nm, Epot=  1.83379e+03 Fmax= 2.62066e+03, atom=
> 1519
> Step=   27, Dmax= 1.4e-02 nm, Epot=  1.41757e+03 Fmax= 5.65049e+02, atom=
> 1513
>
> writing lowest energy coordinates.
>
> Steepest Descents converged to Fmax < 1000 in 28 steps
> Potential Energy  =  1.41757054835921e+03
> Maximum force     =  5.65049499838719e+02 on atom 1513
> Norm of force     =  7.42266925121288e+01
>
> ******************************
> *****************************************************************
>
> I tried a NVT for 500 ps and noticed PE LJ SR are reaching equilibrium
> (plateau after about 100ps). T coupling is working perfectly as well....
>
> Please let me know if my approach/results (picking a convoluted shape
> regardless of equilibrium state) are reliable...
>
> Thank you for your help :)
>
> Also I tried to compress a system of 8 polymers (rather than replicating a
> compressed single chain). As box size becomes less than 3.4 simulation
> crashes but what I need is 3.6nm so I got the desired density. A separate
> folder is included in attached file.(you may compare the results in 2 Excel
> files obtained from these two approaches)
>
> As far as my system is concerned I have no clear idea on the following
> issues:
>
> 1- In general in most of the NPT runs I am not reaching the reference
> pressure ( 50 ,30 ..bar). I get very low values around zero or 1.
> 2-About bond constraints: Actually, in literature I see it is common to fix
> the bond distance. Also in one of the GROMACS tutorials I have seen the
> reasoning that" since bond vibrations are of quantum nature they can not be
> treated classically". The reason you mentioned that I am noy using a good
> force filed is because of using bond constraints or ...? Do I need to remove
> constraints?
>
> 3- I have another inquiry about treating electrostatics contribution in my
> system. My systems as you have noticed involves only C and H. Later I will
> have to solvate this PE chain in HExane which is again apolar (only partial
> charges). It is not still clear to me whether I need to include
> electrostatic energy terms or I need to consider only vdw for calculating
> interaction energies
>
> 4-the value of compressibility I am using in mdp file is 4.5e-5 which is for
> water. I have not found this valued for my polymer yet.
>
> Thanks again, :)
>
>>
>> --
>
> Moeed Shahamat
> Graduate Student (Materials Modeling Research Group)
> McGill University- Department of Chemical Engineering
> Montreal, Quebec H3A 2B2, Canada
> Web:http://mmrg.chemeng.mcgill.ca/pages/current-group-members/moeed-shahamat.php
> Web:http://mmrg.chemeng.mcgill.ca/
>



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