[gmx-users] Discrepancy between -chargegrp and -nochargegrp in simulations with CHARMM ff, Why ?

Francesco Oteri francesco.oteri at gmail.com
Fri Nov 26 11:13:24 CET 2010


To see if the problem is force-field related, you could try to run the 
same simulations using amber-ff.
If you will find the same results, probably is a software bug.

Maybe the bug has been introduced in the version 4 when the Domain 
Decomposition has been introduced.
You can check if it is a software problem using the 3.3.3 version.




Il 25/11/2010 23:42, sa ha scritto:
> Dear All,
>
> In a previous message 
> (http://lists.gromacs.org/pipermail/gmx-users/2010-November/055839.html), 
> I described the results obtained with MD performed with the CHARMM27 
> ff and the chargegrp "yes" and "no" options of a peptide in TIP3P 
> water simulated gromacs. Since these results puzzled me a lot, i would 
> like to share with you others results obtained from the gromacs 
> community advices to explain these results.
>
> In few words, the context of these simulations. One of my labmate did, 
> 8 months ago (march/april), several simulations of a peptide (25 AA) 
> with the CHARMM27 ff (and CMAP). The peptide is a transmembrane 
> segment (TM) and belongs to a large membrane protein. This TM segment 
> has an initial helical conformation. The simulations were performed in 
> a cubic box filled with app. 14000 TIP3P water (Jorgensen's model) 
> with 2 Cl ions. To construct the topology file of the system, 
> -chargegrp "yes" with pdb2gmx and the MD were done with the gromacs 
> 4.0.5. For some reasons, he had to left the lab, and my boss asked me 
> to continue his work. When I checked their results, i was very 
> intrigued by these MD results because he found that the peptide keep 
> along all the simulation time (100 ns) its initial helical 
> conformation. This results are not in agreement with circular 
> dichroism experiments which are shown that the same peptide in water 
> has no helix segment and is completely unfold. I am aware that the 
> simulation time is short compared to experiment time scale, however 
> since i haven't seen any unfolding events in this simulation, so I was 
> not very confident about these results.
>
> To explain this inconsistency, I have suspected that the error came 
> probably of the use of the default -chargegrp with CHARMM ff in these 
> simulations since i have read several recent threads about the charge 
> groups problems in the CHARMM ff implementation in gromacs. To examine 
> this hypothesis I have done two simulations with last gromacs version 
> (4.5.3) and two top files containing charge groups and no charge 
> groups for the peptide residus. I used  the *same* initial pdb file, 
> box size and simulations parameters. The two simulations were carried 
> out during 24 ns in the NPT ensemble with the md.mdp parameters 
> described below after energy minimisation, NVT and NPT equilibration 
> steps.
>
> constraints     = all-bonds
> integrator      = md
> nsteps          = 12000000   ; 24000ps ou 24ns
> dt              = 0.002
>
> nstlist         = 10
> nstcalcenergy   = 10
> nstcomm         = 10
>
> continuation    = no            ; Restarting after NPT
> vdw-type        = cut-off
> rvdw            = 1.0
> rlist                   = 0.9
> coulombtype              = PME
> rcoulomb                 = 0.9
> fourierspacing           = 0.12
> fourier_nx               = 0
> fourier_ny               = 0
> fourier_nz               = 0
> pme_order                = 4
> ewald_rtol               = 1e-05
> optimize_fft            = yes
>
> nstvout         = 50000
> nstxout         = 50000
> nstenergy       = 20000
> nstlog          = 5000          ; update log file every 10 ps
> nstxtcout       = 1000         ; frequency to write coordinates to xtc 
> trajectory every 2 ps
>
> Tcoupl          = nose-hoover
> tc-grps         = Protein Non-Protein
> tau-t           = 0.4 0.4
> ref-t           = 298 298
> ; Pressure coupling is on
> Pcoupl          = Parrinello-Rahman
> pcoupltype      = isotropic
> tau_p           = 3.0
> compressibility = 4.5e-5
> ref_p           = 1.0135
> gen_vel         = no
>
> I found that with charge groups, the peptide remains in its initial 
> helical conformation, whereas with no charge group, the peptide 
> unfolds quickly and has a random coil conformation. I have shown these 
> results to my boss but I was not able to explain why we observe these 
> differences between the two simulations. Indeed since i use PME in the 
> MD, chargegroup should not affect the dynamic results (correct ?) . He 
> asked to do others simulations with different versions of gromacs to 
> see if is not a bug with charge group implementation in gromacs. For 
> testing i have done four others MD wit the *same* initial pdb file, 
> box size and simulations parameters and with previous GMX version 
> 4.5.0 and pre 4.5.2 and with the two types of top files.
>
> In addition since i have done simulations with non optimal parameter  
> for the vdW et electrostatic, i have also tested the influence of the 
> vdW et electrostatic MD parameters on the MD by performing two 
> additional simulations with the parameters  used in the Bjelkmar et al 
> . paper (J. Chem. Theory Comput. 2010, 6, 459–466)  (labeled GMX4.5.3 
> CHARMM in the figures)
>
> ; Run parameters
> integrator      = md            ; leap-frog integrator
> nsteps          = 12000000      ; 2 * 1000000 = 20000 ps
> dt              = 0.002         ; 2 fs
> nstcomm         = 10
> nstcalcenergy   = 10
> ; Output control
> nstxtcout       = 1000         ; frequency to write coordinates to xtc 
> trajectory every 10 ps
> nstxout         = 50000
> nstvout         = 50000         ; save velocities every 0.2 ps
> nstenergy       = 25000         ; save energies every 0.2 ps
> nstlog          = 5000          ; update log file every 0.2 ps
> energygrps      = protein Non-Protein
> ; Bond parameters
> continuation    = yes            ; continuation after NVT
> constraint_algorithm = lincs    ; holonomic constraints
> constraints     = all-bonds     ; all bonds (even heavy atom-H bonds) 
> constrained
> lincs_iter      = 1             ; accuracy of LINCS
> lincs_order     = 4             ; also related to accuracy
> ; Neighborsearching
> ns_type         = grid          ; search neighboring grid cels
> nstlist         = 10            ; 20 fs
> rlist           = 1.2
> ;
> coulombtype              = PME
> rcoulomb-switch          = 0
> rcoulomb                 = 1.2
> vdw-type                 = Switch
> ; cut-off lengths
> rvdw-switch              = 1.0
> rvdw                     = 1.2
> DispCorr                 = EnerPres
> table-extension          = 5
> fourierspacing           = 0.14
> fourier_nx               = 0
> fourier_ny               = 0
> fourier_nz               = 0
> pme_order                = 4
> ewald_rtol               = 1e-05
> ewald_geometry           = 3d
> epsilon_surface          = 0
> optimize_fft             = no
> ; Temperature coupling is on
> tcoupl          = nose-hoover ;
> tc-grps         = protein Non-Protein   ; one coupling groups - more 
> accurate
> tau_t           = 0.4 0.4       ; time constant, in ps
> ref_t           = 297 297       ; reference temperature, one for each 
> group, in K
> ; Pressure coupling is off
> pcoupl          = Parrinello-Rahman             ; pressure coupling in NPT
> pcoupltype      = isotropic
> tau_p           = 3.0
> compressibility = 4.5e-5
> ref_p           = 1.0135
>
> ; Periodic boundary conditions
> pbc             = xyz               ; 3-D PBC
> gen_vel         = no
>
> The results are presented in the three figures accessibles with the 
> three links below
>
> http://img4.hostingpics.net/pics/586637ResultatsVSGMX1jpg.jpg   -> 
> Conformation
> http://img4.hostingpics.net/pics/392578ResultatsVSGMX2jpg.jpg   -> 
> RMSD vs. time
> http://img4.hostingpics.net/pics/271597ResultatsVSGMX3jpg.jpg   -> 
> Secondary structure vs. time
>
> As you can see in all runs with no charge groups option, the peptide 
> quickly unfolds and have a random coil  conformation during the  end 
> of the simulation times, whereas with charge group option, the peptide 
> remains in its initial (helix) conformation whatever the gromacs 
> version used.
>
> To finish I saw that in all the simulation seems to be well conserved
>
> CHARGE GROUP 4.5.3 (along the 24 ns of the run)
>
> Energy                      Average   Err.Est.       RMSD  Tot-Drift
> -------------------------------------------------------------------------------
> Potential                   -561452        5.6    774.891   -1.37923  
> (kJ/mol)
> Total Energy                -455901        5.6    959.234   -1.42286  
> (kJ/mol)
>
> NO_CHARGE GROUP 4.5.3 (along the 24 ns of the run)
>
> Energy                      Average   Err.Est.       RMSD  Tot-Drift
> -------------------------------------------------------------------------------
> Potential                   -563934         18    774.632    -113.02  
> (kJ/mol)
> Total Energy                -458347         18    960.371   -112.951  
> (kJ/mol)
>
> CHARGE GROUP pre4.5.2 (along the 24 ns of the run)
>
> Energy                      Average   Err.Est.       RMSD  Tot-Drift
> -------------------------------------------------------------------------------
> Potential                   -562415        5.1     777.12   -33.8615  
> (kJ/mol)
> Total Energy                -456864        5.1    964.365   -33.7504  
> (kJ/mol)
>
> NO_CHARGE_GROUP_PRE_4.5.2
>
> Energy                      Average   Err.Est.       RMSD  Tot-Drift
> -------------------------------------------------------------------------------
> Potential                   -564899        4.6    778.002   -3.00182  
> (kJ/mol)
> Total Energy                -459312        4.6    963.702   -2.58102  
> (kJ/mol)
>
> NO_CHARGE_GROUP_PRE_4.5.0
>
> Energy                      Average   Err.Est.       RMSD  Tot-Drift
> -------------------------------------------------------------------------------
> Potential                   -563933         30    777.279   -202.641  
> (kJ/mol)
> Total Energy                -458346         29    960.748   -202.578  
> (kJ/mol)
>
> CHARGE_GROUP_PRE_4.5.0
>
> Energy                      Average   Err.Est.       RMSD  Tot-Drift
> -------------------------------------------------------------------------------
> Potential                   -561442          8    773.826   -49.7596  
> (kJ/mol)
> Total Energy                -455891          8    958.546   -49.7573  
> (kJ/mol)
>
> USE_CHARGE_GROUP_AND_GMX_4.5.3 AND CHARMM parameters settings
>
> Energy                      Average   Err.Est.       RMSD  Tot-Drift
> -------------------------------------------------------------------------------
> Potential                   -566048        5.4    765.184   -31.6659  
> (kJ/mol)
> Total Energy                -460851        5.4    950.934   -31.7008  
> (kJ/mol)
>
> USE_NO_CHARGE_GROUP_AND_GMX_4.5.3 AND CHARMM parameters settings
>
> Energy                      Average   Err.Est.       RMSD  Tot-Drift
> -------------------------------------------------------------------------------
> Potential                   -568520         24    770.264   -165.498  
> (kJ/mol)
> Total Energy                -463287         24    955.755   -165.768  
> (kJ/mol)
>
> I am particularly eager to obtain from you some comments and advices 
> about these findings. Thanks you so much for your help.
>
> SA




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