[gmx-users] FEP

Sai Kumar Ramadugu sramadugu at gmail.com
Fri Jun 15 00:52:29 CEST 2012


Hi Fabian,
I am trying something similar with Glutamate to Alanine mutation.
Does your dummy atoms i.e., DUM1 have a value of 0.0 for sigma and epsilon
during all three steps or only in step 2?

Thanks for the time,

Sai

On Thu, Apr 26, 2012 at 10:43 AM, Fabian Casteblanco <
fabian.casteblanco at gmail.com> wrote:

> Hello all,
>
> This is in reply to Michael shirts a while ago on a FEP of a R-CH3 to
> an R-H group.  Below is the orignal email.  I recently tested out
> mutating a CH3-CH3-(3dummy atoms) molecule on both sides in order to
> test out that a peturbation would give you a total of 0.  forcefield
> used was CGenFF
>
> So for procedure was that I turned the CH3 group on the left to an H
> with 3 dummy atoms and I turned an H and 3 dummy atoms on the right to
> a CH3 group, essentially mutating the molecule to another version of
> itself (should give you a total dG of 0 if it works).
>
> STEP 1. (uncharging everything except the -CH2 group inbetween both
> sides  ....   CH3-CH2-HD3)  *D are dummy atoms
>  [ atoms ]
> ;  nr  type  resnr  resid    atom  cgnr  charge    mass    total_charge
>    1    CG331     1   SIM       C1     1        -0.27
>        12.0110         CG331   0.00     12.0110
>    2     HGA3     1   SIM      H11     2         0.09
>        1.00800         HGA3    0.00     1.00800
>    3     HGA3     1   SIM      H12     3         0.09
>        1.00800         HGA3    0.00     1.00800
>    4     HGA3     1   SIM      H13     4         0.09
>        1.00800         HGA3    0.00     1.00800
>    5    CG331     1   SIM       C2     5                -0.27  12.0110
>     CG331
> -0.18    12.0110
>    6     HGA3   1   SIM      H21     6           0.09
>    7     HGA3   1   SIM      H22     7           0.09
>    8     HGA3   1   SIM      H23     8           0.09          1.00800
>     HGA3    0.00     1.00800
>    9      DUM   1   SIM      H31     9           0.00          1.00800
>   10      DUM   1   SIM      H32    10           0.00  1.00800
>   11      DUM   1   SIM      H33    11           0.00          1.00800
>
> STEP 2.  (mutation of groups.           CH3-CH2-HD3 becomes D3H-CH2-CH3)
> [ atoms ]
> ;  nr  type  resnr  resid    atom  cgnr  charge    mass    total_charge
>    1    CG331      1   SIM       C1      1       0.00
>        12.0110         HGA3    0.00       1.00800
>    2     HGA3      1   SIM      H11      2       0.00
>        1.00800         DUM             0.00       1.00800
>    3     HGA3      1   SIM      H12      3       0.00
>        1.00800         DUM             0.00       1.00800
>    4     HGA3      1   SIM      H13      4       0.00          1.00800
>     DUM
>       0.00        1.00800
>    5    CG331      1   SIM       C2      5              -0.18
>    6     HGA3    1   SIM      H21     6                  0.09
>    7     HGA3    1   SIM      H22     7          0.09
>    8     HGA3    1   SIM      H23     8          0.00
>        1.00800         CG331   0.00       12.0110
>    9      DUM    1   SIM      H31     9                  0.00
>  1.00800         HGA3    0.00
>  1.00800
>   10      DUM    1   SIM      H32    10          0.00  1.00800
> HGA3    0.00
>  1.00800
>   11      DUM    1   SIM      H33    11          0.00
>        1.00800         HGA3    0.00       1.00800
>
> STEP3.  (opposite of step1)
> [ atoms ]
> ;  nr  type  resnr  resid    atom  cgnr  charge    mass    total_charge
>    1     HGA3   1   SIM         C1     1         0.00          12.0110
>     HGA3
>  0.09    1.00800
>    2      DUM   1   SIM        H11     2         0.00
> 1.00800         DUM            0.00       1.00800
>    3      DUM   1   SIM        H12     3         0.00
> 1.00800         DUM            0.00       1.00800
>    4      DUM   1   SIM        H13     4         0.00
> 1.00800         DUM            0.00       1.00800
>    5    CG331   1   SIM         C2     5                -0.18
>  12.0110         CG331
>  -0.27   12.0110
>    6     HGA3   1   SIM      H21     6           0.09
>    7     HGA3   1   SIM      H22     7           0.09
>    8    CG331   1   SIM      H23     8           0.00
> 1.00800         CG331     -0.27   12.0110
>    9     HGA3   1   SIM      H31     9           0.00
> 1.00800         HGA3    0.09      1.00800
>   10     HGA3   1   SIM      H32    10           0.00
> 1.00800         HGA3    0.09      1.00800
>   11     HGA3   1   SIM      H33    11           0.00
> 1.00800         HGA3    0.09      1.00800
>
> So in the end, the procedure worked using the g_bar method.  I took 20
> simulations for steps 1 and 3 and 50 simulations for step 2.  Here are
> the results:
>
> Step1: -37.62 +/- 0
> Step2:  -0.12 +/- 0.24
> Step3:  37.68 +/- 0.13
> TOTAL ~ -0.06 kJ/mol  which is expected
>
> My question is that I did something similar for a larger molecule (65
> atoms) and someone said before that step 1 and 3 should be very small.
>  I'm getting values in the near -20 kJ/mol for step 1 and 3.  I feel
> it should be straightforward since I'm simply uncharging a CH3 group
> and I don't get why I'm getting such a large number.  If it is suppose
> to be very small, is it safe to assume that step2 should be a majority
> of the final value.
>
> If anyone has any experience in this area all help is greatly
> appreciated.  Thank you very much.
>
> -Fabian
>
>
>
>
> > So BAR is only
> > referring to the mathematical code used to calculate the overall free
> > energy for the FEP, correct?
>
> Yes.  The information required is the same, with the exception that
> exponential averaging requires energy differences from only one state,
> whereas BAR requires energy differences from both directions.  Since
> you are likely running simulations at a range of states anyway,
> there's no extra cost.
>
> > My question is, for a mutation of a -CH3 group to a -H group, is it
> > better to simply run:
> > [+ from (Lambda=0 ,  R-CH3, full charges and interactions -STATE A)
> > --> (Lambda=1, R-CH, full charges and interactions -STATE B)]
> >
> > OR
> >
> > [1) from (Lambda=0 ,  R-CH3, STATE A : Charges and LJ Interactions: ON)
> > 2)  (Lambda=?, -CH3 Charges: OFF ,LJ Interactions: ON and unmutated)
> > 3)  (Lambda=?, R-CH3, -CH3 Charges: OFF ,LJ Interactions: OFF)
> > 4)  (Lambda=?, R-CH3, -CH3 Charges: OFF ,LJ interactions: ON and Mutated
> to -H)
> > 5)  (Lambda=1, R-CH3, -CH3  STATE B : Charges and LJ Interactions: ON)
>
> Currently, you'd need to run three simulations to do this (will likely
> be simplified somewhat in 4.6).
>
> Set 1: turn R-CH3 charges off in a way that preserves the total charge.
> Set 2: change CH3 LJ to H LJ
> Set 3: Turn R-H charges on in a way that preserves the total charge.
>
> Note that the first and last transformations will need only one two
> states -- their energies will be VERY small.
>
> > Reason I'm asking is because when I try the first choice to do it
> > STATE A to STATE B in one step, when I reach Lambda=0.85 and above on
> > the NVT equilibration right after EM, I receive errors saying that
> > bonds are moving way to far off their constraints which leads me to
> > believe that the system is moving too far from where it was energy
> > minimized.  Errors such as:
> >
> > Step 188, time 0.376 (ps)
> > LINCS WARNING
> > relative constraint deviation after LINCS:
> > rms 0.000017, max 0.000636 (between atoms 9 and 68)
> > bonds that rotated more than 30 degrees:
> >  atom 1 atom 2  angle  previous, current, constraint length
> >      9     68   31.2    0.1111   0.1110      0.1111
> >
> > Step 188, time 0.376 (ps)  LINCS WARNING
> > relative constraint deviation after LINCS:
> > rms 0.000015, max 0.000531 (between atoms 9 and 68)
> > bonds that rotated more than 30 degrees:
> >  atom 1 atom 2  angle  previous, current, constraint length
> >      9     68   31.0    0.1111   0.1110      0.1111
>
> You probably have problems with the charge + LJ terms on the hydrogen.
>  Note that you could possibly use soft core for the Coloumb
> interactions for hydrogen -- it's sometimes causes sampling problems,
> but for H's it probably doesn't matter.  I haven't done this approach
> much so, so I can't tell for sure if it will work.
>
>
> --
> Best regards,
>
> Fabian F. Casteblanco
> Rutgers University --
> Chemical Engineering
> --
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