[gmx-users] rigid tetrahedral molecule

Sanku M msanku65 at yahoo.com
Thu Apr 28 11:07:03 CEST 2011


Thanks Mark for your comment. But, as far as degrees of freedom is concerned, if 
there is a tetrahedral molecule as I shown below with atom #1 ( B) being center 
of the tetrahedron , if we had defined the molecules in terms of bonds and 
angles ( in stead of constraints ), we would have 4 bonds ( 1-2,1-3,1-4,1-5 ) 
and 6 angles ( 2-1-3,2-1-4,2-1-5,3-1-4,3-1-5 , 4-1-5 )at 109.45 degrees  , thus 
total ( 4+6)=10 descriptors .
In that case, the simulation goes fine . But, then wonder, why, for constraints, 
we can put only 9 descriptors .  
Also, I have tried all possible combination to get 9 constraints, but , in each 
case, gromacs crashes. However, defining 4 bonds and 6 angles using high 
force-constant lets the simulation go fine.  So, on a second thought, I wonder 
whether defining 9 bond-constraints to get a stable tetrahedral molecule is at 
all possible. Do I need to go for some sort of compromise,  where 4 bonds 
( 1-2,1-3,1-4,1-5 )  are defined as constraints and 6 angles with high 
force-constant are defined to maintain tetrahedral nature ? 
I am not sure what should be the best possible 9 constraints . 
                      1  opls_1014   1    BF4    B       1      0.8276
     2  opls_1015   1    BF4    F1      1      -0.4569
>>     3  opls_1015   1    BF4    F2      1      -0.4569
>>     4  opls_1015   1    BF4    F3      1      -0.4569
>>     5  opls_1015   1    BF4    F4      1      -0.4569



________________________________
From: Mark Abraham <Mark.Abraham at anu.edu.au>
To: Discussion list for GROMACS users <gmx-users at gromacs.org>
Sent: Thu, April 28, 2011 1:00:42 AM
Subject: Re: [gmx-users] rigid tetrahedral molecule

On 4/28/2011 3:49 PM, Sanku M wrote: 
 I went through the LINCS manual .  But, I am still           struggling with 
coming up with the idea of putting correct           constraint to maintain the 
rigidity of tetrahedral molecule .            I seem to understand  from your 
suggestion that the           tetrahedral can be seen as a combination of  4 
 coupled           triangles.( or am I still wrong about it ?)
I think it's seven coupled triangles, but that's not a relevant way     to think 
about it. You have 5 atoms, so 3N-6 means 9 degrees of     freedom, so you need 
9 independent descriptors of relative atomic     positions, so 9 constraints. 
You were trying 10 and 5.

Because those constraints form triangles, you may need to take care     with 
LINCS to get a stable simulation. Read up on the details here,     I don't 
remember them.


In that case, am I supposed to use multiple settle to keep           the 
molecule in a tetrahedral fashion ? I am sorry but if you           can explain 
it in bit more details, I might get the point.
Forget about SETTLE - it was just an example to illustrate that this     is not 
easy to do right. There's a specialised algorithm for rigid     water (with 
three coupled bond constraints) because it is fiddly to     get such things 
right (and fast).

Mark



________________________________
From: Mark Abraham <Mark.Abraham at anu.edu.au>
>To: Discussion list for GROMACS users <gmx-users at gromacs.org>
>Sent: Wed,               April 27, 2011 11:14:34 PM
>Subject: Re: [gmx-users] rigid tetrahedral molecule
>
>On 4/28/2011 1:54 PM, Sanku M wrote: 
>Hi,
>>  I tried to keep the geometry of the BF4 fixed by                   using 
>>constraints using lincs. But , unfortunately, my                   simulation is 
>>crashing immediately and if I try                   minimization with only 2 
>>molecules, it provides a lot                   of LINCS warning and generate a 
>>lot of step*.pdb file                   . If I try to visualize the minimized 
>>snapshot in VMD,                   it looks like all the distances I tried to 
>>constrain                   decreased drastically. Finally, trying MD run with                   
>>this "minimized" configuration results in crashing due                   to bad 
>>contacts.
>>
>>
>> I am sure I am doing something wrong and it might                   be that my 
>>itp file is wrong . So any help will be                   highly appreciated.
>>Here is the details of what I did.
>>
>>
>>      The geometry of the molecule is tetrahedral                   with B at 
>>the center and 4 F atoms is surrounding it                   in a tetrahedral 
>>manner.
>>I first generated a itp file for BF4 which is shown                   below: I 
>>first got the LJ parameters and charges for B                   and F atom and 
>>put them in ffoplsnb.itp file as new                   atom types opls_1014 
>>and opls_1015 . Initially I tried                   to put contsraint along all 
>>bonds ( i.e among F atoms                   as well ). But, grompp provides 
>>warning that number of                   constraint is more than number of 
>>degrees of freedom.                   So, I reduced number of constraints by 
>>only putting                   constraint among B and F. But, it did not work 
>>either. 
>>
>>
Sure, you need as many constraints as 
http://en.wikipedia.org/wiki/Degrees_of_freedom_%28physics_and_chemistry%29

You should also do your homework about using LINCS and             coupled 
triangles of constraints, as I suggested last time.

Mark


Here is  the .itp file I wrote for rigid BF4 . It                   will be 
great if someone can point me what I am doing                   wrong.
>
>
>  [ moleculetype ]
>; molname       nrexcl
>BF4             3
>
>
>[ atoms ]
>#ifdef _FF_OPLS
>     1  opls_1014   1    BF4    B       1                        0.8276
>     2  opls_1015   1    BF4    F1      1                        -0.4569
>     3  opls_1015   1    BF4    F2      1                        -0.4569
>     4  opls_1015   1    BF4    F3      1                        -0.4569
>     5  opls_1015   1    BF4    F4      1                        -0.4569
>#endif
>[ constraints ]
>  1  2   1   0.146
>  1  3   1   0.146
>  1  4   1   0.146
>  1  5   1   0.146
>  ;  2  3   1   0.238
>;  2  4   1   0.238
>;  2  5   1   0.238
>;  3  4   1   0.238
>;  3  5   1   0.238
>;  4  5   1   0.238
>
>
>[ exclusions ]
>1       2                           3    4  5
>2       1                           3    4  5
>3       1                           2    4  5
>4       1                           2    3  5
>5       1                           2    3  4
>
>
>
>
>
________________________________
From: Mark Abraham <Mark.Abraham at anu.edu.au>
>To: Discussion list for GROMACS users <gmx-users at gromacs.org>
>Sent: Wed, April 27, 2011 8:39:23 PM
>Subject: Re: [gmx-users] rigid tetrahedral molecule
>
>On 4/28/2011 11:25 AM, Justin A. Lemkul wrote:
>> 
>> 
>> Sanku M wrote:
>>> Hi,
>>>  I am interested in simulating a anionic                     molecule BF4(-)  ( 
>>>Boron tetrafluoride).  In the                     paper which developed the 
>>>parameters for this                     molecule, it is mentioned that it has 
>>>been used as                     'rigid' molecule i.e the molecule only has                     
>>>non-bonding interaction but there was no                     intramolecular 
>>>motion as the geometry was fixed.
>>>  I am trying to simulate this molecule in                     gromacs treating 
>>>it as rigid.  But, I was looking                     for best way to 'rigidify' 
>>>this molecule.
>>> 
>>> I was wondering whether using LINCS to                     constrain all B-F 
>>>and F-F bonds will be good enough                     .  Or, Should I use 
>>>virtual sites ? If I really need                     to use virtual site, will 
>>>it be something like TIP5P                     water model ?
>>>  Can someone suggest the best wayout ?
>>> 
>> 
>> Constraints should do the trick, but probably                     the best 
>>approach is to simply contact the authors                     who developed the 
>>model and ask how they did it.                      Then you know you're exactly 
>>reproducing what they                     did.
>
>Yep.
>
>Be aware that the coupled constraints make life                     tricky, and 
>you should read up in the manual and                     literature for how best 
>to use P-LINCS in such                     cases. Algorithms like SETTLE for 
>rigid water exist                     for a reason...
>
>Mark
>
>
>
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