[gmx-users] Heat of vap

Justin A. Lemkul jalemkul at vt.edu
Mon Apr 4 01:32:47 CEST 2011



Elisabeth wrote:
> 
> 
> 
> 
>     Elisabeth wrote:
> 
>         Dear David,
> 
>         I followed your instructions and calculated Heat of vaporization
>         of my alkane once with one molecule in gas phase (no cutoff) and
>         once with equivalent number of molecules as in liquid phase as
>         Justin suggested. Results are as follows:
> 
> 
>     To get heat of vaporization, you shouldn't be simulating just a
>     single molecule in the gas phase, it should be an equivalent number
>     of molecules as you have in the liquid phase.
> 
> Hello David and Justin,
> 
> My explanation was not clear. Below is the results for liquid phase and 
> for gas phase I tried two cases: one single molecule and the other time 
> for equivalent number of molecules as in liquid phase and thats why 
> results are very similar. ( However Justin says one single molecule is 
> not correct. I think when cutoffs is set to zero only bonded terms are 

What is not correct is comparing the potential energy of a liquid system of many 
molecules with a "gas phase" of a single molecule.  Whether or not that was 
something you did still is not entirely clear, but to be very clear, that's what 
I was saying is incorrect to do.  DHvap is based on conversion of equivalent 
systems between liquid and gas.

> treated and even where there are many particles in gas phase to get 

This is incorrect.  Cutoffs of zero mean that all nonbonded interactions are 
calculated, they are not truncated.

> energies per mole of molecules i.e g_energy -nmol XXX must be used so 
> values should be colse to a single molecules case.. please correct me!  
> Anyway results for gas phase are close and this is not the issue now).
> 

You shouldn't need -nmol for any of this.  Simply take the potential energy of 
the two systems (with equivalent numbers of molecules) and apply the formula I 
gave you several emails ago.

-Justin

> Liquid phase:
> 
> Energy                      Average   Err.Est.       RMSD  Tot-Drift
> -------------------------------------------------------------------------------
> LJ (SR)                    -27.3083       0.01   0.296591 -0.0389173  
> (kJ/mol)
> Coulomb (SR)                6.00527     0.0074   0.122878 0.00576827  
> (kJ/mol)
> Coul. recip.                5.59559     0.0032  0.0557413 0.00316957  
> (kJ/mol)
> Potential                   *34.6779  *    0.025    1.03468   -0.11177  
> (kJ/mol)
> Total Energy                86.4044      0.026    1.44353  -0.112587  
> (kJ/mol)
> 
> 
>  
> 
>         *one single molecule in gas phase*
> 
> 
>         Energy                      Average   Err.Est.       RMSD  Tot-Drift
>         -------------------------------------------------------------------------------
>         LJ (SR)                    -2.24473      0.073      1.292  
>         0.342696  (kJ/mol)
>         Coulomb (SR)                11.5723       0.55    2.17577  
>         -2.33224  (kJ/mol)
>         Potential                  *  59.244 *      0.94    10.9756  
>          6.35631  (kJ/mol)
>         Total Energy                106.647          1    15.4828  
>          6.78792  (kJ/mol)
> 
>         *equivalent number of molecules as in liquid* ( large box 20 nm)
> 
>         Statistics over 1000001 steps [ 0.0000 through 2000.0000 ps ], 4
>         data sets
>         All statistics are over 100001 points
> 
>         Energy                      Average   Err.Est.       RMSD  Tot-Drift
>         -------------------------------------------------------------------------------
>         LJ (SR)                    -2.16367      0.053   0.171542  
>         0.374027  (kJ/mol)
>         Coulomb (SR)                11.2894       0.23    0.49105  
>         -1.44437  (kJ/mol)
>         Potential                 *  63.2369    *    1.1    2.47211  
>          7.69756  (kJ/mol)
>         Total Energy                114.337        1.1    2.65547  
>          7.72258  (kJ/mol)
> 
> 
>          Since pbc is set to NO molecules leave the box and I dont know
>         if this all right. I hope the difference is acceptable...!
> 
> 
>     For "pbc = no" there is no box.
> 
> 
>         0- I am going to do the same calculation but for some polymers
>         solvated in the alkane. For binary system do I need to look at
>         nonboded terms? and then run a simulation for a single polymer
>         in vacuum?
> 
>         Can you please provide me with a recipe for Delta Hvap of the
>         solute in a solvent?
> 
> 
>     The method for calculating heat of vaporization is not dependent
>     upon the contents of the system; it is a fundamental thermodynamic
>     definition.  Heat of vaporization is not something that can be
>     calculated from a solute in a solvent.  You can calculate DHvap for
>     a particular system, but not some subset of that system.
> 
>     Thanks Justin. I am interested in the energy required to vaporize
>     the solute in a particular solvent not the whole DHvap of the
>     mixture. do you think this can be achieved by calculating nonbonded
>     energies between solute and solvent? ( defining energy groups ..)
> 
>  
> 
> 
>         1- If I want to look at nonboded interactions only, do I have to
>         add  Coul. recip.  to [ LJ (SR)  + Coulomb (SR) ] ?
> 
> 
>     The PME-related terms contain both solute-solvent, solvent-solvent,
>     and potentially solute-solute terms (depending on the size and
>     nature of the solute), so trying to interpret this term in some
>     pairwise fashion is an exercise in futility.
> 
>     What you mean is when one uses PME interaction energies between
>     components can not be decomposed? So the energy groups I defined to
>     extract nonbonded energies are not giving correct values? Sofar I
>     have been defining energy groups to calculate nonbonded terms
>     between components _A-A A_B... I hope I have not been doing thing
>     wrongly!
> 
> 
> Please help me out!
> 
> Thanks,
> 

-- 
========================================

Justin A. Lemkul
Ph.D. Candidate
ICTAS Doctoral Scholar
MILES-IGERT Trainee
Department of Biochemistry
Virginia Tech
Blacksburg, VA
jalemkul[at]vt.edu | (540) 231-9080
http://www.bevanlab.biochem.vt.edu/Pages/Personal/justin

========================================



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