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| A detailed description of calculations using thermodynamic integration within VASP is given in the supplemental information of reference {{cite|dorner:PRL:2018}} ('''caution''': the tag ''ISPECIAL''=0 used in that reference is not valid anymore, instead the tag {{TAG|PHON_NSTRUCT}}=-1 is used).
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| Using thermodynamic integration the free energy difference between two systems is written as
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| <math> \Delta F = \int\limits_{0}^{1} d\lambda \langle U_{1}(\lambda) - U_{0}(\lambda) \rangle_{\lambda} </math>.
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| Here <math>U_{1}(\lambda)</math> and <math>U_{0}(\lambda)</math> describe the potential energies of a fully-interacting and a non-interacting reference system, respectively. The coupling strength of the systems is controlled via the coupling parameter <math>\lambda</math>. The notation <math>\langle \ldots \rangle_{\lambda}</math> denotes an ensemble average of a system driven by the following classical Hamiltonian
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| <math> H_{\lambda}= \lambda H_{1} + (1-\lambda) H_{0} </math>.
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| The tag {{TAG|SCALEE}} sets the coupling parameter <math>\lambda</math> and hence controls the Hamiltonian of the calculation. | | The tag {{TAG|SCALEE}} sets the coupling parameter <math>\lambda</math> and hence controls the Hamiltonian of the calculation. |
| By default {{TAG|SCALEE}}=1 and the scaling of the energies and forces via the coupling constant is internally skipped in the code. To enable the scaling {{TAG|SCALEE}}<math>\ne</math>1 has to be specified. A VASP calculation outputs the integrand for a given coupling constant at every molecular dynamics step. How to choose the ensemble size and carry out the integration is described in the main text and especially in the supplementary information of reference {{cite|dorner:PRL:2018}}. | | By default {{TAG|SCALEE}}=1 and the scaling of the energies and forces via the coupling constant is internally skipped in the code. To enable the scaling {{TAG|SCALEE}}<math>\ne</math>1 has to be specified. |
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| Two possible options are available for the reference system:
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| *Ideal gas:
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| By default the thermodynamic integration is carried out from the ideal gas to the fully interacting case (in the case when no {{TAG|DYNMATFULL}} is present in the calculation folder). Usually the Stirling approximation is used for the free energy of the ideal gas written as
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| <math> F = -\frac{1}{\beta} \mathrm{ln} \left[ \frac{V^{N}}{\Alpha^{3N} N!} \right] </math>
| | More information using this tag is given [[Thermodynamic integration calculations|here]]. |
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| whre <math>V</math> is the volume of the system, <math>N</math> is the number of particles in the system and <math>\Alpha</math> is the de Broglie wavelength.
| | == Related tags and articles == |
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| *Harmonic solid:
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| If the file {{TAG|DYNMATFULL}} exists in the calculation directory and {{TAG|SCALEE}}<math>\ne</math>1, the second order Hessian matrix is added to the force and thermodynamic integration from a harmonic model to a fully interacting system is carried out. The {{TAG|DYNMATFULL}} file stores the eigenmodes and eigenvalues from diagonalizing the dynamic matrix. This file is written by a previous calculation using the {{TAG|INCAR}} tags {{TAG|IBRION}}=6 and {{TAG|PHON_NSTRUCT}}=-1.
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| == Related Tags and Sections == | |
| {{TAG|VCAIMAGES}}, {{TAG|IMAGES}}, {{TAG|NCORE IN IMAGE1}}, {{TAG|PHON_NSTRUCT}}, {{TAG|IBRION}} | | {{TAG|VCAIMAGES}}, {{TAG|IMAGES}}, {{TAG|NCORE IN IMAGE1}}, {{TAG|PHON_NSTRUCT}}, {{TAG|IBRION}} |
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| == References ==
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| <references/>
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| <noinclude>
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| | | [[Category:INCAR tag]][[Category:Advanced molecular-dynamics sampling]] |
| [[Category:INCAR]][[Category:Molecular Dynamics]][[Category:Thermodynamic integration]] | |
SCALEE = [real]
Default: SCALEE = 1
Description: This tag specifies the coupling parameter of the energies and forces between a fully interacting system and a reference system.
The tag SCALEE sets the coupling parameter 
and hence controls the Hamiltonian of the calculation.
By default SCALEE=1 and the scaling of the energies and forces via the coupling constant is internally skipped in the code. To enable the scaling SCALEE
1 has to be specified.
More information using this tag is given here.
Related tags and articles
VCAIMAGES, IMAGES, NCORE IN IMAGE1, PHON_NSTRUCT, IBRION
