[CP2K-user] [CP2K:18369] Re: Guided AIMD reaction, CONSTRAINT, RESTRAINT, METADYNAMICS

Dobromir A Kalchevski dobromirak at gmail.com
Sat Jan 21 00:00:24 UTC 2023


Dear Marcella Iannuzzi,

Thank you again for the clarifications on sampling final state, finding 
reaction mechanism and potential minimal energy pathway :D This was very 
useful.

Best Regards,
Dobromir

On Friday, January 20, 2023 at 4:00:59 PM UTC+2 Dobromir A Kalchevski wrote:

> This is the colvar:
>
>         &COLVAR
>             &DISTANCE
>                 AXIS XYZ                !DEF XYZ, ANY COMBINATION
>                 ATOMS 50 81
>             &END DISTANCE
>         &END COLVAR
>
> and with restraint it moves the C atom from methane (reacting molecule) to 
> a Si atom in the Si lattice, the way it's supposed to, it just goes too far.
>
> Best Regards,
> Dobromir
>
> On Friday, January 20, 2023 at 3:32:09 PM UTC+2 Marcella Iannuzzi wrote:
>
>>
>> Most probably you defined the COLVAR in the wrong way.
>> If there is an activation barrier in this reaction, this will never 
>> happen in the right way just crashing the molecule into the surface
>>
>> Regards
>> Marcella
>>
>>
>> On Friday, January 20, 2023 at 2:14:26 PM UTC+1 Dobromir A Kalchevski 
>> wrote:
>>
>>> Still, my supervisor doesn't want me to study the FES, he simply wants 
>>> me to make the reaction happen in dynamics. He wants the molecules to move 
>>> around and eventually a reaction to occur.
>>>
>>> Even if I try 
>>>
>>>     &CONSTRAINT
>>>         &COLLECTIVE
>>>             COLVAR 2
>>>             INTERMOLECULAR
>>>             TARGET [angstrom] 5.0                                        
>>>      !initial position in the xyz geometry file
>>>             TARGET_GROWTH [angstrom*fs^-1] 0.01
>>>             TARGET_LIMIT [angstrom] 2.0
>>>         &END COLLECTIVE
>>>     &END CONSTRAINT
>>>
>>> cp2k drives the two atoms from the COLVAR to a distance of 2.0 angstrom 
>>> IMMEDIATELY. Is this normal or is it a bug ?
>>>
>>> And once again, why does RESTAINT with 1 kcal/mol K drive the molecule 
>>> into the surface lattice, pushing lattice atoms around and integrating the 
>>> C atom from the methane into the lattice ? Could it be due to DFTB 
>>> parameterization or is it a bug or am I missing something ?
>>>
>>> Best Regards,
>>> Dobromir
>>> On Friday, January 20, 2023 at 2:35:31 PM UTC+2 Dobromir A Kalchevski 
>>> wrote:
>>>
>>>> Dear Marcella Iannuzzi,
>>>>
>>>> Thank you for your reply.
>>>>
>>>> Best Regards,
>>>> Dobromir
>>>>
>>>> On Friday, January 20, 2023 at 2:21:37 PM UTC+2 Marcella Iannuzzi wrote:
>>>>
>>>>> Dear Dobromir
>>>>>
>>>>> The TARGET is the initial value that is imposed to the variable, as it 
>>>>> is defined. 
>>>>> The TARGET_GROWTH is the rate of change of that target value, which in 
>>>>> the example you posted is ridiculously high:
>>>>>
>>>>> TARGET_GROWTH {Real}
>>>>> *Specifies the growth speed of the target value of the constrained 
>>>>> collective variable.*
>>>>>
>>>>> The constraint with the value determined by the growth rate will be 
>>>>> imposed, no matter which are the other forces in place.
>>>>> At least until the calculation does not converge anymore and 
>>>>> everything explodes.
>>>>>
>>>>> Nothing of this is a sampling in the NVT ensemble, anyway.
>>>>>
>>>>> If the goal is to sample the final state after the reaction has 
>>>>> occurred, just start a simulation from the configuration of the reacted 
>>>>> molecule.
>>>>> If the goal is to find the reaction mechanism, there is no way out of 
>>>>> studying the free energy surface or, in simpler cases, the potential energy 
>>>>> surface. 
>>>>> An efficient way to find  the potential minimal energy pathway in 
>>>>>  cases like yours is in general the nudged elastic band approach.
>>>>>
>>>>> Regards
>>>>> Marcella
>>>>>
>>>>>
>>>>> On Thursday, January 19, 2023 at 9:42:15 PM UTC+1 Dobromir A 
>>>>> Kalchevski wrote:
>>>>>
>>>>>> Hello everyone!
>>>>>>
>>>>>> I want to make a molecule occasionally approach a surface and react 
>>>>>> with it in a NVT ensemble production run. I don't want it fixed in 
>>>>>> predetermined coordinates and I don't want it to fly away or to wait for 
>>>>>> too long of a trajectory.
>>>>>> For now I don't want to study the reaction's thermodynamics. 
>>>>>> Experimentally the reaction occurs.
>>>>>>
>>>>>> I tried the following approaches without success:
>>>>>>
>>>>>> I defined a COLVAR for the distance between one surface atom (Si) and 
>>>>>> the center atom (C) of the gas phase reagent molecule (methane)
>>>>>>
>>>>>>         &COLVAR
>>>>>>             &DISTANCE
>>>>>>                 AXIS XYZ                !DEF XYZ, ANY COMBINATION
>>>>>>                 ATOMS 50 81
>>>>>>             &END DISTANCE
>>>>>>         &END COLVAR
>>>>>>
>>>>>> and then I defined a CONSTRAINT
>>>>>>
>>>>>>     &CONSTRAINT
>>>>>>         &COLLECTIVE
>>>>>>             COLVAR 2
>>>>>>             INTERMOLECULAR
>>>>>>             TARGET [angstrom] 1.87
>>>>>>             TARGET_GROWTH [angstrom*fs^-1] 0.25
>>>>>>             TARGET_LIMIT [angstrom] 5.0
>>>>>>         &END COLLECTIVE
>>>>>>     &END CONSTRAINT
>>>>>>
>>>>>> The result is that both atoms get closer too quickly and the system 
>>>>>> gets an unphysical geometry - the Si kind of moves too far away from it's 
>>>>>> lattice and the C abandons its hydrogens. The remperature rises too quickly 
>>>>>> to unbelievable degrees, the calculation slows down and eventually the 
>>>>>> program dies.
>>>>>> My cell is defined just fine, with enough space for the gas reagent 
>>>>>> to move around. I use a XYZ PBC with space left in one dimension so it 
>>>>>> effectively becomes 2D. In that space is the reacting molecule.
>>>>>> I tried playing with TARGET_GROWTH with many values from 0.01 to 5.0 
>>>>>> and the result is always the same.
>>>>>> In this group I read that the moment TARGET is set the atoms are also 
>>>>>> set at that distance, so I tried switching TARGET and TARGET_LIMIT, but 
>>>>>> even then the result is the same - wrong geometry, they get too close too 
>>>>>> quickly even with very low TARGET_GROWTH, too high temperature - program 
>>>>>> dies.
>>>>>> - Is this a bug, because it makes no sense as expected behavior ?
>>>>>>
>>>>>> I also tried using a RESTRAINT:
>>>>>>
>>>>>>     &CONSTRAINT
>>>>>>         &COLLECTIVE
>>>>>>             COLVAR 2
>>>>>>             INTERMOLECULAR
>>>>>>             TARGET [angstrom] 3.0
>>>>>>             &RESTRAINT
>>>>>>                 K [kcalmol] 1.0
>>>>>>             &END RESTRAINT
>>>>>>         &END COLLECTIVE
>>>>>>     &END CONSTRAINT
>>>>>>
>>>>>> with the COLVAR being a plane between 3 surface atoms:
>>>>>>
>>>>>>         &COLVAR
>>>>>>             &DISTANCE_POINT_PLANE
>>>>>>                 &POINT
>>>>>>                     TYPE GEO_CENTER
>>>>>>                     ATOMS 8
>>>>>>                 &END POINT
>>>>>>                 &POINT
>>>>>>                     TYPE GEO_CENTER
>>>>>>                     ATOMS 21
>>>>>>                 &END POINT
>>>>>>                 &POINT
>>>>>>                     TYPE GEO_CENTER
>>>>>>                     ATOMS 28
>>>>>>                 &END POINT
>>>>>>                 &POINT
>>>>>>                     TYPE GEO_CENTER
>>>>>>                     ATOMS 81
>>>>>>                 &END POINT
>>>>>>                 ATOMS_PLANE 1 2 3
>>>>>>                 ATOM_POINT 4
>>>>>>             &END DISTANCE_POINT_PLANE
>>>>>>         &END COLVAR
>>>>>>
>>>>>> and the gas phase reagent does not stop at the TARGET distance, 
>>>>>> instead it gets inserted into the Si lattice, pushing Si atoms away, 
>>>>>> inserting both C and H from the methane and one of the hydrogens flied far 
>>>>>> away. Temperature goes anomalously high, program slows down, dies. At least 
>>>>>> it took some time and steps to get to the wrong point.
>>>>>> - Why didn't the molecule stop at the surface, while experiencing the 
>>>>>> forces of the lattice atoms ?
>>>>>> - Why did it do beyond the TARGET distance ?
>>>>>> - Is this a bug ?
>>>>>>
>>>>>> Can I use metadynamics in any way to push the molecule towards the 
>>>>>> surface for a reaction to occur ? Once again, I'm not interested in 
>>>>>> studying the FES or the rest of the thermodynamics.
>>>>>>
>>>>>> I just need a way to get the gas phase reagent to occasionally get 
>>>>>> close enough for a reaction.
>>>>>>
>>>>>> I think the answers to those question can be very useful for many.
>>>>>>
>>>>>> I attach some pictures of the anomalous results. The first two are 
>>>>>> from the CONSTRAINT, the 3rd is from the RESTRAINT.
>>>>>>
>>>>>> Best Regards,
>>>>>> Dobromir
>>>>>>
>>>>>

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