MSE 203: Introduction to Computational Materials Engineering

Assignment 3:Ab Initio calculation with Quantum Espresso

Abhishek Kumar
Roll No:22110012

2/04/2024

Problem 1 (25 points)

Using the LDA exchange correlation pseudopotential (pt.rel-pz-n-rrkjus.UPF) and a k-point
mesh of {9 9 9 0 0 0}, i.e., 9x9x9 grid of k-points that are “centered”, study the variation of the
total ground state energy as a function of ecutwfc = 10, 15, 20, 25, 30, 35, 40 Ry with the given k-
point mesh in the input file. When changing the cutoff, make sure to keep the other variables
(lattice constant, k-points, etc.) fixed.
(a)Plot the ground state energy (in eV/atom) as a function of the cutoff energy and estimate the value
for energy convergence. What is the trend that you observe?
Note: this is the preliminary “convergence test” performed for all ab initio calculations, for
determination of an appropriate energy cutoff for all subsequent calculations.
Solution 1:

Figure 1:
Observed trends:
● Initially, energy changes rapidly with increasing cutoff energy.
● After certain points, the rate of energy change decreases, and energy becomes more and more stabilized.
● Finally, the energy reaches a point of convergence that changes little, which means that the energy of the
calculation converges.
Problem 2 (25 points)
Study the variation of the total ground state energy as a function of the k-point mesh: using the
converged value for ecutwfc from above, check for convergence for various grid sizes both
centered and shifted: 3 3 3 0 0 0, 3 3 3 1 1 1, 4 4 4 0 0 0, 4 4 4 1 1 1, etc, all the way up to a
10x10x10 grid. For each grid, record the number of unique k-points after symmetry operations.
This gives a measure of how long your calculation will take - calculations typically scale as K,
where K=number of unique k-points (this can be found in output file “number of k points”). When
changing the size of the k-point grid, make sure to keep your other variables fixed (lattice constant,
cutoff, etc.).
On the same graph, plot the ground state energy as a function of number of unique k-points, for
the two sets of data: centered and shifted grids. What trend do you observe?

Solution2:

Observation:
In conclusion, as the number of k-point increases, the total ground state energy tends to converge to certain
values, and the moving mesh can generally provide more efficient convergence. This trend provides important
guidance in optimizing the accuracy and efficiency of electronic structure calculations.
Problem 3 (25 points)
Study the variation of the total ground state energy as a function of the volume of unit cell (= lattice
parameter cubed), using the converged value for ecutwfc and k-point mesh from Problems 1 and
2. The minimum of the curve will give you the theoretical equilibrium lattice parameter for Pt
corresponding to the pseudopotential used (LDA: pt.rel-pz-n-rrkjus.UPF). When changing the
lattice parameter, make sure to keep your other variables fixed (ecutwfc, k-points, etc.).
Plot the ground state energy as a function of unit cell volume. How do the computed equilibrium
lattice parameter (with LDA) compared with the experimental value of the lattice parameter of Pt?
Note: Lattice parameter needs to be varied judiciously about the mean lattice parameter (which is
known to be close to 7.372 a.u units (=3.9 Angstrom) as given in the input file).

Solution:

Theoretical equilibrium lattice parameter: 4.725 a.u. (equivalent to 2.500 Angstrom)

Experimental lattice parameter of Pt: 3.900 Angstrom.
The computed equilibrium lattice parameter obtained using LDA is significantly larger than the experimental
value of the lattice parameter of Pt. This suggests that the theoretical prediction using LDA may overestimate
the lattice parameter compared to the experimental observation.
Problem 4 (25 points)
MoS2 has gained significant importance in the current industry due to its excellent electronic and
energy storage applications. In this task, explore the materials project repository to access the
structure file of MoS2 in any compatible file format. Further, visualize crystal structure using
Ovito/Vesta and model a 2*2*1 monolayer for further processing.
a) Perform a self-consistent field calculation on the model using the input script MoS2.scf.in and
the suitable pseudo-potential files (Pseudo). Tabulate the first five and last five iterations of self-
consistent field calculation that you observe in the output file and comment on observations.

b) Tabulate the total energy and its contributing energies in percentage, rank them in decreasing
order, and comment on their significance in calculating the total energy.

c) Further, run the job using the script MoS2.bands.in and use the post-processing tool bands.x
on MoS2.bands.pp.in to make data in a readable format. Plot the band structure using the
plotband.x/python to determine the band gap and comment on the nature of band structure.

Solution4:
(a)
Self-Consistent Field Calculation

Iteration Total Energy(Ry) Estimated SCF Accuracy(Ry)

1 -57.59010660 <8.57050849

2 -54.77872259 <90.24384755

3 -63.16434537 <2.12936417

4 -63.34202785 <0.44020923

5 -63.41244093 <0.06571265
 Iteration Total Energy(Ry) Estimated SCF Accuracy(Ry)

14 -63.43558022 <0.000000005

15 -63.43558025 <0.000000002

16 -63.43558025 <9.6E-09

17 -63.43558025 <2.7E-09

18 -63.43558025 <9.64E-12

Observations at the first five iterations:

● Energy volatility: In the initial iteration, the total energy value fluctuates significantly. This indicates that SCF
calculations are the process of finding a stable electronic structure of the system in the early stages.
● Improvement of SCF accuracy: Estimated SCF accuracy decreased significantly from first to fifth. This means
that the calculations are gradually stabilizing and approaching convergence.
Observations at the last five iterations:
● Stability of energy: In the last five iterations, the overall energy value remains almost unchanged and very
stable. This indicates that the SCF calculation has converged successfully.
● Very high SCF accuracy: The estimated SCF accuracy has reached an extremely low level. In particular, the
estimated SCF accuracy at the 18th iteration is <9.64E-12 Ry, which means that the calculation has been
completed with very high precision.
Conclusion:
In the early stages of SCF calculations, there was a significant change in energy and SCF accuracy in the process of
finding the electronic structure of the system. However, as the repetition progressed, the calculations converged
successfully, and in the final stages, very high precision was achieved.
These observations allow SCF calculations to accurately locate the system's stable electronic structure and model
physical phenomena to a reliable level.
 (b) Energy Contribution and its significance

Contribution Explanation Energy(Ry)

One-electron Represent kinetic and potential energy of -23.98193455

non-interacting electrons.

Hartree Accounts for electrostatic repulsion between electrons. 26.32127988

XC Capture electron exchange and correlation effects. -17.93987405

Ewald Accounts for long-range coulomb interactions in -47.83505156

periodic systems.

Total Sum of individual contributions to the total energy. -63.43558027

Energy Contribution and its Percentages

Contribution Energy(Ry) Absolute Percentage(%)

Hartree contribution 26.32127985 41.49

One-electron contribution -23.98193455 37.73

XC contribution -17.93987405 28.31

Ewald contribution -47.83505156 75.35

Total energy -63.43558027 XXX

1. Importance of Ewald Contribution:

importance: Ewald contribution has the largest share of total energy at 75.35. This means that long-distance coulomb
interactions in systems with periodic boundary conditions have a huge impact on overall energy. In particular, in solid
physics or crystal structure analysis, this interaction is an important factor that cannot be ignored.
Impact on overall energy calculation: If long-distance interaction is not accurately considered, the calculation of
total energy can be greatly distorted. Thus, Ewald contributions play a key role in accurately predicting total energy.

2. Importance of Hartree Contribution:

importance: Hartree contributions account for 41.49% of total energy. This indicates that the electrostatic repulsive
force between electrons makes an important contribution to the entire energy. Interaction between electronic clouds is a
major factor in determining energy conditions.
Impact on overall energy calculation: By considering the interaction between electrons, you can understand the
stability and structure of the system more accurately. Without Hartree contributions, it is difficult to accurately predict
the distribution and energy minimization of electronic clouds.
3. Importance of One-Electron Contribution:
importance: One-electron contribution accounts for 37.73% of total energy. This means that the motor and position
energy of the unprotected electrons is an important part of the overall energy calculation.
Impact on overall energy calculation: Understanding the behavior of basic electrons is the basis for predicting the
energy state of the entire system. These contributions are important for establishing the basic characteristics of the
electronic structure.

4. Importance of XC Contribution:
importance: XC contribution accounts for 28.31% of total energy. Electronic exchange and correlation effects capture
the subtle effects that electrons encounter when they are close to each other. This is especially important when the
former is dense.
Impact on overall energy calculation: Accurately modeling the exchange correlation effect is essential to predict the
state of energy minimization and obtain an accurate electronic structure. This plays an important role in understanding
the chemical properties and reactivity of a substance.

(C) Band Structure

Band gap determination

In the band structure plot, the energy difference between the lowest point of the conduction and the highest
point of the magnetosphere is the band gap. The size of this gap plays an important role in determining
whether a substance is a metal, semiconductor, or insulator.

● Direct band gap: If the lows of the conductivity and the highs of the magnetosphere occur at the same
k-value, the material is said to have a direct band gap. This has a significant impact on optical properties,
which means that the absorption and emission of light can occur efficiently.
● Indirect band gap: If the lows of the conductivity and the highs of the magnetosphere occur at different
k-values, it is said to be an indirect band gap. Substances with indirect band gaps may have less optical
properties than substances with direct band gaps.
Band structure properties:
Through detailed analysis of the band structure, a deep understanding of the electronic properties of the material can be
obtained:

● Effective mass of electrons: In the band structure, the curvature of the strip is related to the effective mass of
the former. If the strip is very flat, the effective mass of the electron is large, and the mobility is low.
Conversely, if the belt is steep, the effective mass of the former is small, and the mobility is high.
● Valley: An area with deep curvature formed by conductors and gargles around a specific k-point is called a
valley. In valley electronics, these valleys can play an important role in the dynamic properties of electrons.
● Spin-orbit bond (SOC): The effect of spin-orbital bonds on certain substances may appear in the band
structure, which can lead to phenomena such as spin splitting.

By analyzing the band structure obtained experimentally or computationally, you can gain important insights into the
electronic properties and potential applications of substances such as MoS2. MoS2, for example, is an electron and
optoelectronic cow due to its promising semiconductor properties.