[gmx-users] question of perturbing order in single topology FEP, gromacs

asaffarhi at post.tau.ac.il asaffarhi at post.tau.ac.il
Sun Dec 3 08:49:50 CET 2017


Hi Peng,

You can compare the relative free energy with the other topology to  
see which order probably gives you the correct results. I don't know  
what is your project and for free energies associated with bonds where  
the atom (Carbon or Oxygen) is without nonbonded interactions there  
are analytic results

http://iopscience.iop.org/article/10.1088/1367-2630/18/2/023039/meta

Best,
Asaf

Quoting Peng He <hepeng.yanglu at gmail.com>:

> Hi, Asaf,
>
> I totally agreed what you suggested, but I am considering the bonded energy
> term changing in the free energy simulation in the single topology, I have
> read the paper you suggested and it is using a dual topology method which
> also works well in my case, in the single topology method, the bond
> equilibrium length is changing according to lambda values. for example, in
> ethane -> methanol case, the shrinking(changing the bonded lambdas) of cc
> bond to co bond(the second carbon is changing to oxygen gradually and
> shares one atom in the topology file) is gonna affect the 1,4 electrostatic
> interaction of hydrogens connecting to carbon and carbon/oxygen center.
> While in dual topology there is no such problem because the charge is only
> disappearing and appearing with no position change. I am wondering if the
> single topology method relies on the order of perturbation a lot and which
> order is the most correct way.
>
> Best
> Peng
>
> 2017-11-30 9:27 GMT-05:00 <asaffarhi at post.tau.ac.il>:
>
>> Dear Peng,
>>
>> There are several ways to do it.
>>
>> The simplest way is to take each molecule and perturb it separately. You
>> have one Ethane molecule and one methanol molecule so you need a file
>> containing only Ethane and a file containing only methanol.
>>
>> The different atoms between the molecules are CH3 in Ethane and OH in
>> methanol.
>> In each molecule you can remove the VDW and Coul terms of these atoms in
>> transformations. That's all. See Fig. 9.
>> The transformed systems should be identical in their remaining nonbonded
>> terms and bonded terms relating the common atoms so an additional minor
>> transformations may be needed.
>>
>> There may be some issues related to changing the total charge in
>> transformations, which can cause artificial changes in the calculated free
>> energies.
>>
>> Best regards,
>>
>> Asaf
>>
>>
>> Quoting Peng He <hepeng.yanglu at gmail.com>:
>>
>> Hi, Asaf,
>>>
>>> Thank you very much for your suggestions, I am not sure I understand it
>>> correctly.
>>>
>>> 2017-11-29 13:22 GMT-05:00 <asaffarhi at post.tau.ac.il>:
>>>
>>> Dear Peng,
>>>>
>>>> You can transform each of the molecules seperately.
>>>>
>>>
>>> You can remove the nonbonded interactions of the atoms that are different
>>>
>>>> between the compared molecules.
>>>>
>>>> Does it mean when going from A-B to A-C, decouple the B's nonbonded than
>>> coupling the C's nonbonded interaction?
>>>
>>> Then, if you have only one dihedral relating the different atoms to the
>>>> common atoms in each molecule it does not need to be removed. Also, the
>>>> bond angle and covalent bond terms do not need to be removed. This is
>>>> based
>>>> on NVT but may be also accurate for NPT.
>>>>
>>>> In the Ethane -> methanol case, the C-C bond length decreases from 1.5 to
>>> 1.4 when perturbing to C-O bond, and the kappa for the bond also changes,
>>> I
>>> am not sure but I think we can use bonded lambdas to perturb the bond, I
>>> did not remove any bond or angle in this case.
>>> I think what you suggest is dual topology method which contains a dummy
>>> CH3
>>> group in Methanol and a dummy OH group in Ethane, in that case I don't
>>> need
>>> to change the bond length and angle, and it would not create such
>>> different
>>> free energy values. I really test it in dual topology method and there is
>>> little effect from the order of perturbations.
>>>
>>>>
>>>> We also saw that the order of transforming matters but maybe you can try
>>>> without removing the bonded terms.
>>>>
>>>
>>>
>>> For more details you can read:
>>>> http://www.sciencedirect.com/science/article/pii/S0010465516303411
>>>>
>>>> Best,
>>>> Asaf
>>>>
>>>>
>>>> Quoting Peng He <hepeng.yanglu at gmail.com>:
>>>>
>>>> HI, all,
>>>>
>>>>>
>>>>> I am recently doing some test FEP calculations to get familiar, I am
>>>>> preparing a system of ethane -> methanol using Amber gaff force field
>>>>> and
>>>>> single topology method.
>>>>>
>>>>> "  4 [ atomtypes ]
>>>>>   5 ;name   bond_type     mass     charge   ptype   sigma
>>>>>  epsilon
>>>>>     Amb
>>>>>   6  c3       c3          0.00000  0.00000   A     3.39967e-01
>>>>> 4.57730e-01 ; 1.91  0.1094
>>>>>   7  hc       hc          0.00000  0.00000   A     2.64953e-01
>>>>> 6.56888e-02 ; 1.49  0.0157
>>>>>   8  oh       oh          0.00000  0.00000   A     3.06647e-01
>>>>> 8.80314e-01 ; 1.72  0.2104
>>>>>   9  h1       h1          0.00000  0.00000   A     2.47135e-01
>>>>> 6.56888e-02 ; 1.39  0.0157
>>>>>  10  dh       hc          0.00000  0.00000   A     0.00000  0.00000
>>>>>  11  ho       ho          0.00000  0.00000   A     0.00000e+00
>>>>>  0.00000e+00
>>>>>  12 [ moleculetype ]
>>>>>  13 ;name            nrexcl
>>>>>  14  UNK              3
>>>>>  15
>>>>>  16 [ atoms ]
>>>>>  17 ;   nr  type  resi  res  atom  cgnr     charge      mass       ;
>>>>> qtot
>>>>> bond_type
>>>>>  18      1   c3     1   UNK    C1    1    -0.095100     12.01000   c3
>>>>>  0.116700    12.01000
>>>>>  19      2   c3     1   UNK    C2    2    -0.095100     12.01000   oh
>>>>> -0.598801    12.01000
>>>>>  20      3   hc     1   UNK    H1    3     0.031700      1.00800   h1
>>>>>  0.028700     1.00800
>>>>>  21      4   hc     1   UNK    H2    4     0.031700      1.00800   h1
>>>>>  0.028700     1.00800
>>>>>  22      5   hc     1   UNK    H3    5     0.031700      1.00800   h1
>>>>>  0.028700     1.00800
>>>>>  23      6   hc     1   UNK    H4    6     0.031700      1.00800   ho
>>>>>  0.396000     1.00800
>>>>>  24      7   hc     1   UNK    H5    7     0.031700      1.00800   dh
>>>>>  0.000000     1.00800
>>>>>  25      8   hc     1   UNK    H6    8     0.031700      1.00800   dh
>>>>>  0.000000     1.00800
>>>>>  26
>>>>>  27 [ bonds ]
>>>>>  28 ;   ai     aj funct   r             k
>>>>>  29      1      2   1    1.5375e-01    2.5179e+05  1.4233e-01
>>>>> 2.6501e+05
>>>>>  30      1      3   1    1.0969e-01    2.7665e+05  1.0969e-01
>>>>> 2.7665e+05
>>>>>  31      1      4   1    1.0969e-01    2.7665e+05  1.0969e-01
>>>>> 2.7665e+05
>>>>>  32      1      5   1    1.0969e-01    2.7665e+05  1.0969e-01
>>>>> 2.7665e+05
>>>>>  33      2      6   1    1.0969e-01    2.7665e+05  9.7300e-02
>>>>> 3.1079e+05
>>>>>  34      2      7   1    1.0969e-01    2.7665e+05  1.0969e-01
>>>>> 2.7665e+05
>>>>>  35      2      8   1    1.0969e-01    2.7665e+05  1.0969e-01
>>>>> 2.7665e+05
>>>>> ...
>>>>> ..."
>>>>>
>>>>> I know to perturbing from large molecule(ethane) to small(methanol), I
>>>>> need
>>>>> to perturb the electrostatic interaction first than vdw, But I don't
>>>>> know
>>>>> where to perturb the bonded lambdas. I have tested different orders of
>>>>> Bonded lambdas, and I have got a quite different answer which seems odd
>>>>> to
>>>>> me. I have a table for that
>>>>> stage1 stage2 stage3 dG(kj) dG(kcal)
>>>>> single topology solv q/bonded/vdw -14.36 -3.43
>>>>> bonded q vdw -13.79 -3.30
>>>>> bonded/q vdw -14.91 -3.56
>>>>> q bonded vdw -17.13 -4.09
>>>>> q bonded/vdw -20.22 -4.83
>>>>> q vdw bonded -25.2 -6.02
>>>>> single topology vac q/bonded/vdw 10.32 2.47
>>>>> bonded q vdw 9.53 2.28
>>>>> bonded/q vdw 9.1 2.17
>>>>> q bonded vdw 8.71 2.08
>>>>> q bonded/vdw 9.64 2.30
>>>>> q vdw bonded 9.84 2.35
>>>>> The desolvation free energy of ethane is -2.48 and methanol 3.48kcal.
>>>>> The best result which close the cyclo for ethane,vac -> ethane, solv ->
>>>>> methanol, solv -> methanol,vac -> ethane,vac is perturbing all three
>>>>> together(q/bonded/vdw) followed by perturbing bonded/q together then
>>>>> vdw.
>>>>> The worst is to decouple bonded lambdas the last. When I try dual
>>>>> topology
>>>>> method, there is no such difference where to place the bonded lambdas...
>>>>>
>>>>>  I am confused that which one should used and why others are not OK?
>>>>>
>>>>> Thank you
>>>>> Best
>>>>> Peng
>>>>> --
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>>>>
>>>>
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