DFT-D2: Difference between revisions
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In the DFT-D2 method of Grimme{{cite|grimme:jcc:06}}, the correction term takes the form: | In the DFT-D2 method of Grimme,{{cite|grimme:jcc:06}} activated by setting {{TAG|IVDW}}=1 or 10 (or the obsolete {{TAG|LVDW}}=''.TRUE.''), the correction term takes the form: | ||
:<math>E_{\mathrm{disp}} = -\frac{1}{2} \sum_{i=1}^{N_{at}} \sum_{j=1}^{N_{at}} \sum_{\mathbf{L}} {}^{\prime} \frac{C_{6ij}}{r_{ij,L}^{6}} f_{d,6}({r}_{ij,\mathbf{L}}) </math> | :<math>E_{\mathrm{disp}} = -\frac{1}{2} \sum_{i=1}^{N_{at}} \sum_{j=1}^{N_{at}} \sum_{\mathbf{L}} {}^{\prime} \frac{C_{6ij}}{r_{ij,L}^{6}} f_{d,6}({r}_{ij,\mathbf{L}}) </math> | ||
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:<math>f_{d,6}(r_{ij}) = \frac{s_6}{1+e^{-d(r_{ij}/(s_R\,R_{0ij})-1)}}</math> | :<math>f_{d,6}(r_{ij}) = \frac{s_6}{1+e^{-d(r_{ij}/(s_R\,R_{0ij})-1)}}</math> | ||
whereby the global scaling parameter <math>s_6</math> has been optimized for several different DFT functionals such as PBE (<math>s_6=0.75</math>), BLYP (<math>s_6=1.2</math>) or B3LYP (<math>s_6=1.05</math>). The parameter <math>s_R</math> is usually fixed at 1.00. | whereby the global scaling parameter <math>s_6</math> has been optimized for several different DFT functionals such as PBE (<math>s_6=0.75</math>), BLYP (<math>s_6=1.2</math>) or B3LYP (<math>s_6=1.05</math>). The parameter <math>s_R</math> is usually fixed at 1.00. | ||
Optionally, the damping function and the vdW parameters can be controlled using the following flags (the given values are the default ones): | |||
*{{TAG|VDW_RADIUS}}=50.0 : cutoff radius (in <math>\AA</math>) for pair interactions | *{{TAG|VDW_RADIUS}}=50.0 : cutoff radius (in <math>\AA</math>) for pair interactions | ||
Revision as of 14:28, 24 February 2025
In the DFT-D2 method of Grimme,[1] activated by setting IVDW=1 or 10 (or the obsolete LVDW=.TRUE.), the correction term takes the form:
- [math]\displaystyle{ E_{\mathrm{disp}} = -\frac{1}{2} \sum_{i=1}^{N_{at}} \sum_{j=1}^{N_{at}} \sum_{\mathbf{L}} {}^{\prime} \frac{C_{6ij}}{r_{ij,L}^{6}} f_{d,6}({r}_{ij,\mathbf{L}}) }[/math]
where the first two summations are over all [math]\displaystyle{ N_{at} }[/math] atoms in the unit cell and the third summation is over all translations of the unit cell [math]\displaystyle{ {\mathbf{L}}=(l_1,l_2,l_3) }[/math] where the prime indicates that [math]\displaystyle{ i\not=j }[/math] for [math]\displaystyle{ {\mathbf{L}}=0 }[/math]. [math]\displaystyle{ C_{6ij} }[/math] denotes the dispersion coefficient for the atom pair [math]\displaystyle{ ij }[/math], [math]\displaystyle{ {r}_{ij,\mathbf{L}} }[/math] is the distance between atom [math]\displaystyle{ i }[/math] located in the reference cell [math]\displaystyle{ \mathbf{L}=0 }[/math] and atom [math]\displaystyle{ j }[/math] in the cell [math]\displaystyle{ L }[/math] and the term [math]\displaystyle{ f(r_{ij}) }[/math] is a damping function whose role is to scale the force field such as to minimize the contributions from interactions within typical bonding distances. In practice, the terms in the equation for [math]\displaystyle{ E_{\mathrm{disp}} }[/math] corresponding to interactions over distances longer than a certain suitably chosen cutoff radius (VDW_RADIUS, see below) contribute only negligibly to [math]\displaystyle{ E_{\mathrm{disp}} }[/math] and can be ignored. Parameters [math]\displaystyle{ C_{6ij} }[/math] and [math]\displaystyle{ R_{0ij} }[/math] are computed using the following combination rules:
- [math]\displaystyle{ C_{6ij} = \sqrt{C_{6ii} C_{6jj}} }[/math]
and
- [math]\displaystyle{ R_{0ij} = R_{0i}+ R_{0j}. }[/math]
The values for [math]\displaystyle{ C_{6ii} }[/math] and [math]\displaystyle{ R_{0i} }[/math] are tabulated for each element and are insensitive to the particular chemical situation (for instance, [math]\displaystyle{ C_6 }[/math] for carbon in methane takes exactly the same value as that for C in benzene within this approximation). In the DFT-D2 method, a Fermi-type damping function is used:
- [math]\displaystyle{ f_{d,6}(r_{ij}) = \frac{s_6}{1+e^{-d(r_{ij}/(s_R\,R_{0ij})-1)}} }[/math]
whereby the global scaling parameter [math]\displaystyle{ s_6 }[/math] has been optimized for several different DFT functionals such as PBE ([math]\displaystyle{ s_6=0.75 }[/math]), BLYP ([math]\displaystyle{ s_6=1.2 }[/math]) or B3LYP ([math]\displaystyle{ s_6=1.05 }[/math]). The parameter [math]\displaystyle{ s_R }[/math] is usually fixed at 1.00.
Optionally, the damping function and the vdW parameters can be controlled using the following flags (the given values are the default ones):
- VDW_RADIUS=50.0 : cutoff radius (in [math]\displaystyle{ \AA }[/math]) for pair interactions
- VDW_S6=0.75 : global scaling factor [math]\displaystyle{ s_6 }[/math] (available in VASP.5.3.4 and later)
- VDW_SR=1.00 : scaling factor [math]\displaystyle{ s_R }[/math] (available in VASP.5.3.4 and later)
- VDW_SCALING=0.75 : the same as VDW_S6 (obsolete as of VASP.5.3.4)
- VDW_D=20.0 : damping parameter [math]\displaystyle{ d }[/math]
- VDW_C6=[real array] : [math]\displaystyle{ C_6 }[/math] parameters ([math]\displaystyle{ \mathrm{Jnm}^{6}\mathrm{mol}^{-1} }[/math]) for each species defined in the POSCAR file
- VDW_R0=[real array] : [math]\displaystyle{ R_0 }[/math] parameters ([math]\displaystyle{ \AA }[/math]) for each species defined in the POSCAR file
- LVDW_EWALD=.FALSE. : the lattice summation in [math]\displaystyle{ E_{\mathrm{disp}} }[/math] expression is computed by means of Ewald's summation (.TRUE. ) or via a real space summation over all atomic pairs within cutoff radius VDW_RADIUS (.FALSE.). (available in VASP.5.3.4 and later)
The performance of PBE-D2 method in optimization of various crystalline systems has been tested systematically in reference [2].
| Important: It is recommended to use the more advanced and more accurate method DFT-D3.[3] |
Mind:
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Related tags and articles
VDW_RADIUS, VDW_S6, VDW_SR, VDW_SCALING, VDW_D, VDW_C6, VDW_R0, LVDW_EWALD, IVDW, DFT-ulg, DFT-D3, DFT-D4