VASP Structure Optimization

1. Input Files

The input files for VASP are the four basic files: INCAR, POSCAR, POTCAR, KPOINTS.

1.1 INCAR Parameter Settings

System = Si-film    # System name, can be freely defined to identify the current calculation system.

# Job Control
ISTART = 0          # Initial state setup:
                    # 0 Start calculation from scratch.
                    # 1 Read initial wavefunctions from WAVECAR file.
                    # 2 Read wavefunctions and charge density from WAVECAR and CHGCAR files.
ISPIN = 1           # Spin polarization options:
                    # 1 Non-spin-polarized (for non-magnetic materials).
                    # 2 Spin-polarized (for magnetic materials).
ICHARGE = 2         # Initial charge density selection:
                    # 2 Start from static charge density provided by POTCAR.
                    # 1 Generate charge density from scratch.
LWAVE = .FALSE.     # Output WAVECAR file:
                    # .TRUE. Output (store wavefunction data).
                    # .FALSE. Do not output (save disk space).
LCHARG = .FALSE.    # Output CHGCAR file:
                    # .TRUE. Output (store static charge density).
                    # .FALSE. Do not output (save disk space).
ISYM = 0            # Symmetry settings:
                    # 0 Disable symmetry (for systems with defects or asymmetric structures).
                    # 1 or 2 Preserve symmetry operations.

# Electronic Relaxation
ENCUT = 500         # Plane-wave cutoff energy (eV), determines calculation precision and efficiency.
ISMEAR = 0          # Smearing method:
                    # -5 (tetrahedron method for metals), 0 (Gaussian smearing for semiconductors), 1 or 2 (Fermi smearing).
SIGMA = 0.05        # Smearing width (eV), recommended values: 0.01 ~ 0.1.
EDIFF = 1E-08       # SCF convergence criterion: stops if energy change between iterations is less than 1E-08 eV.
NELMIN = 6          # Minimum number of electronic iterations to ensure basic convergence.
NELM = 300          # Maximum number of electronic iterations to avoid iteration loops.
GGA = PE            # Functional choice, using PBE (Perdew-Burke-Ernzerhof) exchange-correlation functional.
LREAL = .FALSE.     # Reciprocal space calculations, increases precision but adds computational cost.
ADDGRID = .TRUE.    # Enable additional FFT grid for improved numerical accuracy.
ALGO = N            # Electronic relaxation algorithm:
                    # Normal (standard mode), Fast, or VeryFast (accelerated modes).
PREC = Accurate     # Precision settings:
                    # Accurate (high precision), Normal, or Low (for initial tests).

# Ionic Relaxation
ISIF = 2            # Lattice optimization options:
                    # 2 Optimize atomic positions only, keep lattice parameters fixed.
                    # 3 Optimize both atomic positions and lattice shape.
EDIFFG = -0.01      # Ionic convergence criterion:
                    # Negative values based on force (eV/\u00c5).
                    # Positive values based on energy.
IBRION = 2          # Ionic relaxation algorithm:
                    # 2 Conjugate gradient algorithm (suitable for most optimization tasks).
POTIM = 0.5         # Time step, controls optimization speed.
NSW = 200           # Maximum number of ionic steps.

# Parallel Control
NPAR = 4            # FFT grid parallelization dimension (recommended: sqrt(total cores)).
KPAR = 2            # Number of parallel k-points (total cores should be divisible by NPAR \u00d7 KPAR \u00d7 NCORE).
NCORE = 12          # Number of cores per task.

For structural optimization, key parameters in INCAR include IBRION, ISIF, NSW, EDIFF, and EDIFFG.

1.1.1 Common IBRION Settings and Applications

(1) Single-Point Energy Calculation

• IBRION = -1
  Usage: Used for single-point energy calculations such as fixed lattice, electronic structure, or DOS analysis.
  Note: Avoid setting NSW > 0 to prevent wasting resources.

(2) Structure Optimization

• IBRION = 1 (RMM-DIIS)
  Usage: Suitable for smooth potential energy surfaces in simple systems.
  Limitation: May encounter convergence issues for complex or unstable surfaces.

• IBRION = 2 (Conjugate Gradient)
  Usage: Most commonly used method, suitable for most systems.
  Advantage: Performs well for steep and complex surfaces.

• IBRION = 3 (Damped Molecular Dynamics)
  Usage: Stabilizes optimization paths that oscillate or diverge.

(3) Molecular Dynamics

• IBRION = 0
  Usage: For studying dynamic behavior of systems at different temperatures, such as diffusion or vibrational modes.

(4) Phonon Calculations

a. Finite Difference Method IBRION = 5, 6
Calculates phonon modes using finite difference:

• 5: Without symmetry, suitable for defective or low-symmetry structures.
• 6: Exploits symmetry for efficient calculations in high-symmetry systems.

b. Perturbation Theory (DFPT) IBRION = 7, 8
Calculates phonon modes using density functional perturbation theory (DFPT):

• 7: Without symmetry optimization, suitable for low-symmetry structures.
• 8: Utilizes symmetry for faster computation.

1.1.2 Common ISIF Settings and Applications

• Default value (if not set): ISIF = 2 (Optimize atomic positions only, keep lattice shape and volume fixed).

• Special Cases:
  • IBRION = 0 (molecular dynamics) or LHFCALC = .TRUE. (hybrid functional): ISIF = 0.

• ISIF = 2 (Most Common)
  Optimizes atomic positions only, suitable for 2D materials, fixed lattice constants, or surface/interface systems.

• ISIF = 3 (Bulk Optimization)
  Optimizes atomic positions, lattice shape, and volume, suitable for bulk material relaxations.

• ISIF = 4 (Fixed Volume Optimization)
  Optimizes atomic positions and lattice shape while keeping the volume fixed, useful for pressure tests.

• ISIF = 6 (Lattice-Only Optimization)
  Optimizes lattice shape and volume without relaxing atomic positions, useful for testing lattice parameters.

• ISIF = 0 (Position Optimization, No Stress Calculation)
  Optimizes atomic positions without calculating stress, for fixed cell optimizations.

1.1.3 Recommended Settings for NSW, EDIFF, and EDIFFG

Parameter	Function	Initial Optimization	High-Precision Optimization	Single Point
NSW	Max ionic steps	100-200	200-500	0
EDIFF	SCF convergence (eV)	1e-05	1e-08	1e-06
EDIFFG	Ionic convergence (eV/\u00c5)	-0.1	-0.01	Not required

1.2 Example POSCAR

Below is an example POSCAR file describing the structure of bulk silicon:

Si-bulk   # System name, customizable
1.0       # Global scaling factor (can be used to scale the lattice)
   5.430    0.000    0.000  # Lattice vector a
   0.000    5.430    0.000  # Lattice vector b
   0.000    0.000    5.430  # Lattice vector c
Si           # Atom types
2            # Number of atoms for each type
Direct       # Coordinate type (Direct: fractional; Cartesian: cartesian)
  0.000  0.000  0.000  # Coordinates for atom 1
  0.250  0.250  0.250  # Coordinates for atom 2

Example POSCAR File for Silicon Thin Film (Si-film):

Si Thin Film                            
   1.00000000000000     
     5.4299999999999997    0.0000000000000000    0.0000000000000000
     0.0000000000000000    5.4299999999999997    0.0000000000000000
     0.0000000000000000    0.0000000000000000   20.8599999999999994
   Si
    16
Selective dynamics  # Enable Selective Dynamics
Direct
0.000000 0.000000 0.200000 F F F  # Fixed in all three directions
0.500000 0.500000 0.200000 T T F  # Fixed in z-direction, free in x and y
0.500000 0.000000 0.330153 T T T  # Free in all directions
0.000000 0.500000 0.330153 T T T
0.250000 0.250000 0.265077 T T T
0.750000 0.750000 0.265077 T T T
0.750000 0.250000 0.395230 T T T
0.250000 0.750000 0.395230 T T T
0.000000 0.000000 0.460307 T T T
0.500000 0.500000 0.460307 T T T
0.500000 0.000000 0.590460 T T T
0.000000 0.500000 0.590460 T T T
0.250000 0.250000 0.525384 T T T
0.750000 0.750000 0.525384 T T T
0.750000 0.250000 0.655537 T T T
0.250000 0.750000 0.655537 T T T

1.3 KPOINTS File

(1) Monkhorst-Pack Grid

Monkhorst-Pack grids provide a uniform k-point distribution for periodic crystal calculations.

Automatic k-point generation   # Automatic k-point generation method (comment)
0                              # Ignore total k-point count, use automatic generation
Monkhorst-Pack                 # Choose Monkhorst-Pack grid
4 4 4                          # Grid density in x, y, z directions
0 0 0                          # No grid shift

Use Case: Periodic crystals, optimization, DOS calculations, and electronic structure analysis.

(2) Gamma Grid

Gamma grids center the k-point grid at the Gamma point, suitable for small or asymmetric lattices.

Automatic k-point generation   # Automatic k-point generation method (comment)
0                              # Ignore total k-point count, use automatic generation
Gamma                          # Choose Gamma-centered grid
4 4 4                          # Grid density in x, y, z directions
0 0 0                          # No grid shift

Use Case: Small systems, asymmetric lattices, or fast calculation optimization tasks.

1.4 POTCAR File Usage

POTCAR contains pseudopotential information required to describe atomic properties in the system.

VASP Provides Multiple Types of Pseudopotentials:

• POT_GGA_PAW: PAW pseudopotentials with GGA functional.
• POT_LDA_PAW: PAW pseudopotentials with LDA functional.

Generating the POTCAR File:

For a system with atoms like Si and H, concatenate the pseudopotential files:

cat /POT_GGA_PAW/POTCAR_Si /POT_GGA_PAW/POTCAR_H > POTCAR

• Ensure the functional type in POTCAR matches the INCAR settings.
• Maintain the atom order in POTCAR consistent with the element order in POSCAR.

2. Output Files

2.1 CONTCAR File

Content: Optimized crystal structure, including updated atomic coordinates and lattice parameters. Format: Same as POSCAR, can directly serve as input for further calculations. Use Case:

• Review the final optimized crystal structure.
• Use for further calculations (e.g., band structure, DOS).

2.2 OSZICAR File

Content:

• Brief record of SCF (Self-Consistent Field) iteration energy changes.
• Energy (E0, dE) for each SCF step.
• Convergence information for SCF.
• Total energy changes per ion step during optimization.

Use Case:

• Quickly check SCF calculation or optimization convergence.
• Decide if adjustments to EDIFF or optimization steps are necessary.

2.3 OUTCAR File

Content:

• Most detailed output file with complete calculation history.
• Includes parameters like electronic relaxation, iteration info, convergence criteria, etc.
• Energy, force, stress, atomic coordinates for each optimization step.
• Charge density info (if applicable).

Use Case:

• Analyze convergence details and energy/force variations during optimization.

2.4 XDATCAR File

Content:

• Atomic coordinates for each ionic step during optimization or molecular dynamics (MD).

Use Case:

• Analyze atomic movement paths during optimization.
• Perform trajectory analysis for structural changes.

2.5 vasprun.xml File

Content: XML-formatted record of all calculation data, suitable for parsing and post-processing.

• Includes electronic iteration, ionic optimization parameters, and results.
• Data for energy, force, stress, atomic coordinates, etc.

Use Case:

• Extract key information using tools like pymatgen or ASE.

3. Optimization Process and Convergence Criteria

3.1 Optimization Process

1. Initialization of the Structure:
   • The initial structure is provided through the POSCAR file.
   • The optimization conditions are configured using the POTCAR, KPOINTS, and INCAR files.
2. Stepwise Optimization:
   • After each ionic optimization step, the total energy, atomic forces, and lattice stress of the system are recalculated.
   • The optimization continues until convergence criteria (e.g., EDIFFG) are satisfied or the maximum number of steps (NSW) is reached.
3. Structure Updates:
   • Intermediate results of each optimization step are stored in the XDATCAR file.
   • The final structure after optimization is saved in the CONTCAR file.

3.2 Convergence Criteria

The convergence of the optimization process can be determined using the following methods:

1. OUTCAR File:

   • Check whether the force on each atom is less than

     EDIFFG

     .

   • Verify whether the total energy change is less than EDIFF.
2. OSZICAR File:
   • Review the energy changes (E0 and dE) during the SCF iterations.
   • Determine whether the SCF process has stabilized and converged.
3. CONTCAR File:
   • Extract the final optimized atomic positions and lattice parameters.
   • If the optimization has not converged, the CONTCAR file contains the structure from the last step.
4. Using Tools:
   • Use tools like pymatgen or ASE to parse the vasprun.xml file and evaluate convergence.

3.3 Common Issues and Solutions

3.3.1 SCF Not Converging

Issue: SCF iterations show energy oscillations or divergence.

Possible Causes:

• The initial electronic density is poorly set.
• Insufficient cutoff energy (ENCUT).

Solutions:

• Increase the maximum number of SCF iterations by setting NELM=200.
• Raise the cutoff energy: increase ENCUT to 520 eV or higher.

3.3.2 Optimization Not Converging

Issue: Optimization reaches the maximum steps (NSW) but does not meet convergence criteria for force or energy.

Possible Causes:

• The initial structure is far from the energy minimum.
• Convergence criteria (EDIFFG) are too strict.
• The optimization step size (POTIM) is too large.

Solutions:

• Provide a reasonable initial structure or pre-optimize using external tools.
• Relax the convergence criteria: adjust EDIFFG from -0.01 to -0.02.
• Reduce the optimization step size: adjust POTIM from 0.5 to 0.2.

3.3.3 Oscillations During Optimization

Issue: Energy and forces oscillate repeatedly during optimization, preventing stable convergence.

Possible Causes:

• The optimization step size (POTIM) is too large.
• The optimization algorithm is unsuitable for the system.

Solutions:

• Decrease the optimization step size: set POTIM to 0.2 or smaller.
• Change the optimization algorithm:
  • Use the conjugate gradient method by setting IBRION=2.
  • Use damped molecular dynamics by setting IBRION=3.

3.3.4 Divergence During Optimization

Issue: Severe deformation of the structure occurs during optimization, leading to significant energy increases.

Possible Causes:

• Atomic distances are too short due to an unreasonable initial structure.
• Inadequate vacuum spacing (for low-dimensional systems such as thin films or nanostructures).
• Incorrect pseudopotential files.

Solutions:

• Ensure reasonable initial atomic distances to avoid overly close atoms.
• Increase the vacuum spacing: for low-dimensional systems, set the vacuum layer thickness to at least 15 Å.
• Verify the POTCAR file to ensure the pseudopotential matches the atomic species.