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用VASP计算VDW

已有 7309 次阅读 2017-4-16 16:45 |个人分类:我的学习笔记|系统分类:科研笔记| VASP, vdw

VASP手册里关于VDW的说明:

建议用 optPBE-vdW, or the optB88-vdW functional,比较精确(Peng Feng)




http://cms.mpi.univie.ac.at/vasp/vasp/vdW_DF_functional_Langreth_Lundqvist_et_al.html


vdW-DF functional of Langreth and Lundqvist et al.

The vdW-DF proposed by Dion et al. [143] is a non-local correlation  functional that approximately accounts for dispersion interactions. In VASP the method is implemented using the algorithm of Roman-Perez  and Soler [144] which transforms the double real space integral to reciprocal space and reduces the computational effort. Several propsed versions of the method can be used: the original vdW-DF [143], the ``opt" functionals (optPBE-vdW, optB88-vdW, and optB86b-vdW) where the exchange functionals  were optimised for the correlation part [145],  and the vdW-DF2 of Langreth and Lundqvist groups [146].

This method is available since the 5.2.12.26May2011 version of VASP for the calculation of  total energies and forces. The stress calculation for the cell optimisation (ISIF=3) is available since the VASP 5.2.12.11Nov2011 version for spin unpolarised systems and VASP 5.3.1  for spin polarised systems.

N.B.: This feature has been implemented by J. Klimeš. If you make use of the vdW-DF functionals presented in this section, we ask you to cite Ref. [147]. Please also cite the original vdW-DF paper of Dion et al. [143] and the paper of Roman-Perez and Soler [144]. In addtion, cite the paper of Lee et al. [146] if you use the vdW-DF2 functional, the paper of Klimeš et al. [145] if you use the optB88-vdW or optPBE-vdW functionals, and any other appropriate references, such as Ref. [148].

 
Correlation functionals

The method is invoked by setting

LUSE_VDW = .TRUE.

Moreover, the PBE correlation correction needs to be removed since only LDA correlation is used in the functionals. This is done by setting

AGGAC = 0.0000

The two tags above need to be used for all of the following functionals.

 
Exchange functionals

The GGA tag is further used to choose the appropriate exchange functional. The original vdW-DF of Dion et al uses revPBE, therefore the vdW-DF can be chosen  by setting

GGA = RELUSE_VDW = .TRUE.AGGAC = 0.0000

More accurate exchange functionals for the vdW correlation functional have been proposed in [145] and [147]. To use these functionals set:

GGA = ORLUSE_VDW = .TRUE.AGGAC = 0.0000

for optPBE-vdW,

GGA = BOPARAM1 = 0.1833333333PARAM2 = 0.2200000000LUSE_VDW = .TRUE.AGGAC = 0.0000

for the optB88-vdW functional, or

GGA = MK PARAM1 = 0.1234 PARAM2 = 1.0000LUSE_VDW = .TRUE.AGGAC = 0.0000

for the optB86b-vdW functional.

In the vdW-DF2 functional the rPW86 exchange functional is used

GGA = ML

moreover, the vdW functional needs to be changed to the vdW2 correlation which requires only a change of a parameter:

Zab_vdW = -1.8867

Therefore to use vdW-DF2, set:

GGA = MLLUSE_VDW = .TRUE.Zab_vdW = -1.8867AGGAC = 0.0000

An overview of the performance of the different approaches can be found  for example in [145,146] for gas phase clusters and in [147] for solids.

 
Important remarks:

  • The method needs a precalculated kernel which is distributed via the VASP download portal (VASP -> src -> vdw_kernel.bindat) and on the ftp server (vasp5/src/vdw_kernel.bindat). If VASP does not find this file, the kernel will be calculated. This, however,  is rather demanding calculation. The kernel needs to be either copied to  the VASP run directory for each calculation or can be stored in a central  location and read from there. The location needs to be set in routine  PHI_GENERATE. This does not work on some clusters and the kernel needs to be copied into the run directory in such cases. The distributed file uses little endian convention and won't be read on big endian machines. The big endian version of the file is available from the VASP team.  

  • There are no special POTCARs for the vdW-DF functionals and the PBE or LDA POTCARs can be used.  Currently the evaluation of the vdW energy term is not done fully within the PAW method but the sum of the pseudo-valence density and partial core density is used. This approximation works rather well, as is discussed in [147], and the accuracy generally increases when the number of valence  electrons is increased or when harder PAW datasets are used. For example, for adsorption it is recommended to compare the adsorption energy obtained with  standard PAW datasets and more-electron POTCARs for both PBE calculation  and vdW-DF calculation to assess the quality of the results.

  • The spin polarised calculations are possible, but strictly speaking the non-local vdW correlation is not defined for spin-polarised systems. For spin-polarised calculation the non-local vdW correlation energy is evaluated on the sum of the spin-up and spin-down densities.

  • The evaluation of the vdW energy requires some additional time. Most of it is spent on performing FFTs to evaluate the energy and potential.  Thus the additional time is determined by the number of FFT grid points in the  calculation, basically size of the simulation cell. It is almost independent on the number of the atoms in the cell. Thus the relative cost of the vdW-DF method depends on the ``filling" of the cell and increases with the amount of vacuum in the cell. The relative increase is high for isolated molecules  in large cells, but small for solids in smaller cells with many k-points.

C( graphite ) +2I2 = CI4 我在没有考虑VDW的情况下算出反应的形成焓是正的,与预期相反。想着应该是CI4 为分子,应考虑VDW的影响。同时,对于反应中的其它物质也应该考虑VDW。


                                                           ∆H = +2.7077      non

                                                          H =+ 2.75386    optPBE_VDW

                                                         H= + 2.70642    optB88_VDW

考虑VDW(non)和考虑时(用两种算法), 单个结构的焓值有很大变化,但是反应的形成焓差别不大。总体来讲,这个反应的形成焓就是正值。




























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