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I am trying to calculate the band structure of a TiO2-Rutile slab, but the result I got is not very smooth, and the result shows it is an indirect gap material, but the bulk phase of TiO2-Rutile is a direct gap material. My question is:

  1. Is it possible that the energy gap of the material is direct in the bulk but indirect in the slab?
  2. Is it normal that the band structure of a slab is not smooth? I can see the result of Ni 100 surface bandstructure on the vasp tutorial, it seems also not very smooth.

Here are the INCAR,POSCAR and KPOINTS files I use:

System=TiO2 surface DOS #Startparameter for this run: ISTART =1 #job :0-new 1-continue 2-samecut charge:0-initial ICHARG =11 #charge:0-initial orbitals 1-from CHGCAR 2-ISTART=0 superposition of atoms #Electronic Properties ISMEAR =1 #part.occupancies -5-Blochl -4-tetra -1-fermi 0-guas;when calculate band,don't use ISMEAR=-5 conductor-1 semiconductor and insulator-0 SIGMA =0.05 #broadening in eV, when calculate Band structure, ISMEAR, SIGMA use default values ISPIN =2 #spin polarized calculation? 1-no 2-yes default-2 LORBIT = 11 #Electronic Relaxation PREC =Accurate ENCUT =520 #energy cutoff in eV: Default-largest ENMAX from POTCAR-file EDIFF =0.1E-04 #stopping-criterion for ELM NELM =100 #the maximum number of electronic SC steps,default=60 NELMIN =3 #the minimum number of electronic SC steps,default=2 # NELMDL =3 #number of non-selfconsistent steps at the begining，default=5-10 #DOS NEDOS =2000 EMIN =-10 EMAX =10 #Write file or not? # LWAVE =.FALSE. #write WAVECAR,default= .TRUE. # LCHARG =.FALSE. #write CHG/CHGCAR,default= .TRUE. #Ionic relaxation # EDIFFG =0.1E-03 #stopping-criterion for IOM, default: EDIFFG = EDIFF×10 # NSW =200 #number of steps for IOM. 0-default # IBRION =2 #ionic relax: ionic relaxation: 0-MD 1-quasi-New 2-CG # ISIF =2 #stress and relaxation, when IBRION=0, ISIF=0,other default values is 2. # POTIM =0.10 #time-step for inoic-motion # LREAL =.FALSE. #.TRUE.=true space .FALSE.=reciprocal space = default. #Parallelization flags NCORE=8 #KPAR=6 
TiO2_mp-2657_computed\(1\1\0) 1.0 2.9691998959 0.0000000000 0.0000000000 0.0000000000 6.5806999207 0.0000000000 0.0000000000 0.0000000000 40.7333984375 Ti O 10 20 Direct 0.500000000 0.000000000 0.129769996 0.500000000 0.500000000 0.210549995 0.500000000 0.000000000 0.291330010 0.500000000 0.500000000 0.372099996 0.500000000 0.000000000 0.452879995 0.000000000 0.500000000 0.129769996 0.000000000 0.000000000 0.210549995 0.000000000 0.500000000 0.291330010 0.000000000 0.000000000 0.372099996 0.000000000 0.500000000 0.452879995 0.500000000 0.304580003 0.129769996 0.500000000 0.804579973 0.210549995 0.500000000 0.304580003 0.291330010 0.500000000 0.804579973 0.372099996 0.500000000 0.304580003 0.452879995 0.500000000 0.695420027 0.129769996 0.500000000 0.195419997 0.210549995 0.500000000 0.695420027 0.291330010 0.500000000 0.195419997 0.372099996 0.500000000 0.695420027 0.452879995 0.000000000 0.000000000 0.098200001 0.000000000 0.500000000 0.178979993 0.000000000 0.000000000 0.259759992 0.000000000 0.500000000 0.340530008 0.000000000 0.000000000 0.421310008 0.000000000 0.000000000 0.161339998 0.000000000 0.500000000 0.242119998 0.000000000 0.000000000 0.322899997 0.000000000 0.500000000 0.403679997 0.000000000 0.000000000 0.484450012 
Special k-points for band structure 10 ! intersections line-mode reciprocal 0.0000000000 0.0000000000 0.0000000000 1 GAMMA 0.5000000000 0.0000000000 0.0000000000 1 X 0.5000000000 0.0000000000 0.0000000000 1 X 0.5000000000 0.5000000000 0.0000000000 1 S 0.5000000000 0.5000000000 0.0000000000 1 S 0.0000000000 0.5000000000 0.0000000000 1 Y 0.0000000000 0.5000000000 0.0000000000 1 Y 0.0000000000 0.0000000000 0.0000000000 1 GAMMA

Here is the result I got:

OUTCAR -> NSPIN = 2; NKPTS = 40; NBANDS = 150; Efermi = -2.8040 ------------------------------------------------------ SPIN_UP SPIN_DN ------------------------------------------------------ IND 111 111 CBM ENG -1.63250 -1.63220 KPT 0.5000 0.5000 0.0000 0.5000 0.5000 0.0000 ____________________________________________ IND 110 110 VBM ENG -2.81420 -2.83650 KPT 0.1667 0.5000 0.0000 0.1111 0.0000 0.0000 ____________________________________________ GAP 1.18170 1.20430 inDirect_Gap inDirect_Gap 1.18170 inDirect_Gap

enter image description here

An update after a new test, if I use 40 intersections between two special points. The band structure looks better obviously.
enter image description here

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    $\begingroup$ In KPOINTS file, you set 10 as a number of intersections between two special points. It is small one. It is better to increase to 25 or 30. $\endgroup$ Commented Dec 23, 2021 at 14:45

2 Answers 2

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You should take Binh Tien's advice for the continuity part of your problem. It has also been answered somewhat here:

How to ensure a smooth band structure?

As for the gap issue, adding to Phil Hasnip's answer, a similar question has also had several proposals for answers here :

How to generate the high symmetry paths for band structure calculations?

These might be enough for you to fix your issue.

Allow me to stress again on the fact that, "The 2D slab does not have the same symmetry as the full 3D slab, and there is no requirement for the conduction band minima and valence band minima to be at the same points in reciprocal-space"

Don't forget to give that green checkmark for the answers that help you resolve your issue and to comeback and tell us how you did it yourself so that we can close out this issue !

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1. Is it possible that the energy gap of the material is direct in the bulk but indirect in the slab?

Yes, this is possible (as is the reverse). The 2D slab does not have the same symmetry as the full 3D slab, and there is no requirement for the conduction band minima and valence band minima to be at the same points in reciprocal-space. As you make the slab thicker and thicker, you would usually expect to recover the properties of the 3D bulk materials, although strictly speaking the symmetry is not fully recovered whilst it is only 2D-periodic.

2. Is it normal that the band structure of a slab is not smooth?

No, this is not physically sensible. The curvature of the band in reciprocal-space is related to the particle's effective mass, $m$, by

\begin{align} \left[m^{-1}\right]_{ij} = \frac{1}{\hbar^2} \frac{\partial^2 E}{\partial k_i \partial k_j}. \end{align}

Except for a fully localised band, the effective mass should be finite. The jagged, non-differentiable parts of your band-structure are artefacts of the calculation or plotting. This is probably due to the finite sampling of k-points (10 is not very many for such a small real-space cell), and I expect they would disappear if you used more intermediate points or a larger real-space cell. Note that your cell has an in-plane aspect ratio of approximately 1:2 so the k-points are spaced twice as far apart in one direction, and this is where the bands appear most jagged.

Jagged band-structures can also be artefacts of the plotting software, which usually joins bands together based simply on their energy, rather than the corresponding physical state. Using additional information, such as band-gradients or projections, can allow a more physical matching of states across the Brillouin zone, and improve the quality of the plot.

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  • $\begingroup$ Is it usual that the slab and bulk of the same material have different gap type? Or usually, they are the same? $\endgroup$ Commented Dec 23, 2021 at 16:57
  • $\begingroup$ I don't know, but it certainly happens for several materials. It will also depend on the thickness of the slab, and any surface passivation or reconstruction you have. $\endgroup$ Commented Dec 23, 2021 at 21:13

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