METHODS FOR ELECTRONIC

STRUCTURE CALCULATIONS
Presented by Harshith Reddy
Classification of
Methods

0 Quantum Mechanical Methods

1
0 Molecular Mechanics Methods
2
0 Hybrid Methods
3
0 Semi-Empirical Methods
4
 Hartree fock theory
1. Introduction to Hartree-Fock Theory
The Hartree-Fock (HF) method is a fundamental quantum mechanical approach used to approximate the wavefunction
of a many-electron system. It simplifies the complex interactions between electrons by employing a mean-field
approximation, effectively allowing the calculation of electronic structure in atoms and molecules.

2. Theoretical Foundation
2.1) Wavefunction Approximation
HF theory approximates the many-body wavefunction of a system as a single Slater determinant. This determinant is
constructed from the single-particle wavefunctions (orbitals) of the electrons. The Slater determinant ensures that the
overall wavefunction remains antisymmetric, adhering to the Pauli exclusion principle.

2.2) Self-Consistent Field (SCF) Method

The HF method utilizes a self-consistent field approach, where the effective potential acting on each electron is
averaged over the positions of all other electrons. This results in a set of coupled equations, known as the Hartree-Fock
equations, which need to be solved iteratively until convergence is reached. The energy expression for the HF method
can be represented as: here Where T is the kinetic energy operator and Vee is the electron-electron interaction
operator.
 Strengths and limitations
3. Strengths and Limitations
3.1) Wavefunction Approximation
• Computational Efficiency: HF theory is computationally faster than many post-Hartree-Fock methods due to its
reliance on a single Slater determinant, allowing it to handle relatively large systems efficiently.
• Foundation for Other Methods: It serves as a starting point for more advanced methods that incorporate electron
correlation, such as Møller-Plesset perturbation theory and coupled-cluster methods.
3.2) Limitations
• Neglect of Electron Correlation: A major drawback of HF theory is its inability to account for electron correlation
effects adequately. This limitation leads to inaccuracies, especially in systems where electron interactions are
significant, such as in transition states and bond-breaking scenarios.
• Inability to Describe Certain Properties: The HF method may struggle with predicting certain properties like reaction
energies and molecular geometries accurately, particularly in cases where electron correlation plays a critical role.

3. Applications
Hartree-Fock theory is widely used in computational chemistry for studying molecular structures, reaction
mechanisms, and the electronic properties of various chemical systems. It is often implemented in software packages
like Gaussian and ORCA, providing a foundation for understanding electronic structure in molecules.In summary,
Hartree-Fock theory is a vital tool in quantum chemistry that provides a valuable approximation for the electronic
structure of many-electron systems. Despite its limitations, its computational efficiency and foundational role in more
advanced methods make it indispensable in computational studies.

Sherrill, C. D. (2000). An Introduction to Hartree-Fock

 Density Field Theory
Overview of DFT
Density Functional Theory (DFT) is a quantum mechanical method that has become a cornerstone in computational
chemistry and materials science for calculating the electronic structure of many-body systems. Unlike traditional
wavefunction-based methods, which rely on the many-body wavefunction to describe the quantum state of a system,
DFT focuses on the electron density as the primary variable. This shift simplifies the complex many-body problem,
significantly reducing computational requirements and making DFT suitable for a wide range of systems, from small
molecules to large and complex materials.
Theoretical Foundations
The foundation of DFT is built upon two pivotal theorems proposed by Hohenberg and Kohn.
• First Hohenberg-Kohn Theorem: This theorem asserts that the ground state properties of a many-electron system
are uniquely determined by its electron density. In practical terms, this means that rather than requiring the full
wavefunction, which depends on a vast number of variables, one can derive all observable properties of the system
solely from the electron density.
• Second Hohenberg-Kohn Theorem: This theorem introduces the Kohn-Sham framework, which allows for the
practical implementation of DFT. It involves mapping the interacting electron system which repel each other onto a
system of non-interacting fictitious particles that reproduce the same electron density. The Kohn-Sham equations
govern this system and are central to DFT calculations.The Kohn-Sham equation is expressed as:

where Veff​ is the effective potential, incorporating the external potential and the interaction between electrons. The
solution of this equation is carried out self-consistently, meaning that the output electron density is fed back into the
calculations to refine the potential until convergence is achieved.
 Exchange-Correlation Energy
A critical component of DFT is the treatment of electron-electron interactions through the exchange-correlation energy,
denoted as Exc​. The accuracy of DFT calculations is heavily influenced by the choice of exchange-correlation
functional. Common functionals include:
• Local Density Approximation (LDA): This functional assumes that the electron density is uniform over a small region,
simplifying calculations by using density values at a point.
• Generalized Gradient Approximation (GGA): This approach accounts for the gradient of the electron density, providing
better accuracy for systems where density varies significantly.
• Hybrid Functionals: Such as B3LYP, these combine elements of DFT with Hartree-Fock methods, leading to improved
performance in specific applications.
Computational Efficiency
DFT is known for its computational efficiency, scaling as O(N^3), where NNN is the number of electrons. This efficiency
allows researchers to perform calculations on significantly larger systems than traditional wavefunction methods would
allow. DFT is particularly advantageous in fields such as materials science, catalysis, and biochemistry, where large
numbers of atoms are often involved.
Applications in Materials Science
DFT has extensive applications in materials science. Researchers leverage DFT to study electronic properties,
structural stability, and reactivity of various materials. Key applications include:
• Band Structure Calculations: Understanding the energy levels of electrons in solids, which is crucial for
semiconductor design.
• Density of States: Analyzing the distribution of electron states, informing about the electrical and thermal properties
of materials.
• Molecular Geometries: Optimizing structures of complex molecules and materials, aiding in the development of
Imperial College London. (n.d.). Density Functional
 Møller–Plesset Perturbation Theory
Overview of Møller Perturbation Theory
Møller Perturbation Theory is a method in quantum mechanics that helps us study systems when an exact
solution is difficult to obtain. Instead of tackling the whole system directly, MPT allows us to treat certain
interactions as "small perturbations" to a simpler system that we can solve exactly.
Perturbation: In this context, a perturbation is a small change or interaction that modifies the Hamiltonian (the
operator that corresponds to the total energy of the system). This theory assumes that the Hamiltonian can be
split into two parts: a simple, solvable part and a small additional part that we want to understand.
Theoretical Foundations
The Hamiltonian H is the core operator in quantum mechanics that governs the dynamics of a system. MPT posits
that

• H0​: This is the unperturbed Hamiltonian, representing a system that we can solve exactly (like a hydrogen
atom).
• V: This is the perturbation, which represents a small change or interaction that we want to account for (like an
external electric field).
• λ: This small parameter indicates the strength of the perturbation. When λ=0, we revert to the unperturbed
system.
• The idea is to express the properties of the perturbed system as a series expansion in terms of λ. This means
that we start with the known solution and add corrections due to the perturbation.
 Møller–Plesset Perturbation Theory
Energy Corrections
To understand how the perturbation affects the energy of the system, we look at the energy levels of the
unperturbed system and calculate corrections.
Zeroth-Order Energy:
The energy of the unperturbed system is denoted by E(0)n .These are the energy levels obtained from solving H0
For example, if H0 is the Hamiltonian for a hydrogen atom, En(0)​ would give the energy levels for the hydrogen
atom without any external influences.
First-Order Energy Correction:
The first-order correction to the energy is given by:
Interpretation: This equation states that the first-order energy correction depends on the expectation value of the
perturbation V in the unperturbed state ψn(0)​. In simpler terms, it means we are taking the average effect of the
perturbation on the unperturbed state.
Second-Order Energy Correction:
The second-order correction is more complex and accounts for the effects of all other states:

• Interpretation: This equation sums the contributions from all other states m (that are not n). The numerator
represents how much the perturbation connects states m and n. The denominator ​ measures how different
the energies of these states are. A larger difference means a smaller contribution to the correction.
 Møller–Plesset Perturbation Theory
Wave Function Corrections

Just like the energy levels, the wave functions also experience corrections due to the perturbation. The first-order
correction to the wave function is given by:

Applications and Limitations

Møller Perturbation Theory is highly useful in quantum chemistry and condensed matter physics:
• Applications:
⚬ It is applied to study atomic and molecular interactions, electron correlation effects, and transitions
between different states of matter.
⚬ For example, MPT can help predict how the energy levels of an atom change when subjected to an
external electromagnetic field.
• Limitations:
⚬ MPT is most effective when the perturbation is small. If the perturbation is not small or if the system
behaves in a non-linear manner (i.e., not adequately described as a series expansion), MPT may fail to
provide accurate results.
⚬ In such cases, alternative methods, such as non-perturbative techniques or numerical simulations, might
be necessary.

Møller, C., & Plesset, M. S. (1934). Note on the Perturbation

 Coupled Cluster Theory
Coupled Cluster Theory
Overview
Coupled Cluster (CC) theory is a sophisticated method in quantum chemistry used for calculating the electronic
structure of many-body systems. It is particularly valued for its accuracy in describing correlated electron
interactions, which are crucial for understanding molecular systems.
Fundamental Principles
At the core of CC theory lies the concept of correlation. In quantum systems, electrons are not independent; they
interact with each other, leading to correlations that affect their behavior. CC theory addresses these correlations
by expanding the many-body wavefunction in terms of an exponential ansatz. The wavefunction Ψ can be
expressed as:

where Φ0 is a reference wavefunction (often the Hartree-Fock state), and T is the excitation operator that
accounts for
Excitation electron correlation by including excitations from the reference state
Operators
The excitation operator T is typically divided into singles (T1) and doubles (T2​). Singles involve promoting one
electron, while doubles involve promoting two electrons. The full CC wavefunction is built upon these excitations:
T=T1+T2+… The CC approach provides an efficient way to account for these excitations, allowing for a systematic
improvement in accuracy with increasing complexity.
Computational Efficiency
Despite its high accuracy, CC theory is computationally demanding. However, it is often more efficient than traditional
methods because it can accurately describe electron correlations without the need for an extensive basis set.
 Configuration Interaction
Overview
Configuration Interaction (CI) is a quantum mechanical method used in computational chemistry to account for
electron correlation in molecular systems. It enhances the accuracy of wavefunction-based methods by
considering multiple electron configurations, thereby providing a more comprehensive view of the electronic
structure.
Concept of Electron Configuration
In quantum mechanics, the state of a system of electrons can be described by a wavefunction, which is
constructed from various electron configurations. Each configuration corresponds to a different arrangement of
electrons in atomic or molecular orbitals. The simplest approach, known as Hartree-Fock (HF), approximates the
electron correlation by treating electrons independently. However, this fails to capture the effects of electron-
electron interactions accurately.
The CI Approach
CI improves upon HF by incorporating excitations from the reference configuration (usually the HF solution). It
does this by forming a linear combination of the reference configuration and several excited configurations. The
general CI wavefunction can be expressed as:
where Φ0 is the reference configuration and Φi are the excited configurations. The coefficients cic_ici​ determine
the contribution of each configuration to the overall wavefunction.
Types of CI
There are various CI methods, including CI singles (CIS), CI doubles (CID), and Full Configuration Interaction (FCI).
CIS considers single excitations only, while CID includes double excitations. FCI takes into account all possible
excitations and provides the most accurate results but at a high computational cost.
 Force Fields in Molecular
Mechanics
Molecular mechanics (MM) is a computational approach that models the physical movements of atoms and molecules
using classical physics. Unlike quantum mechanical methods, which solve the Schrödinger equation for electron
interactions, molecular mechanics operates under the principles of classical mechanics, focusing on the interactions
between atoms based on their positions, charges, and other properties. This approach is particularly useful for
studying large biological systems, polymers, and complex materials where quantum methods may be computationally
prohibitive.
Understanding Force Fields
Force fields are the mathematical representations of the interactions between atoms in molecular mechanics. A force field defines how
atoms within a molecule or a set of molecules interact with each other by specifying the potential energy associated with various atomic
arrangements. This potential energy is expressed as a function of the positions of the atoms, allowing for the calculation of molecular
configurations and energies. The force field consists of various terms that describe different types of interactions:
1.Bond Stretching: Energy changes when two bonded atoms move from their equilibrium bond length. A harmonic potential models
this, with repulsion when atoms are too close and attraction when they’re too far.
2. Angle Bending: Describes energy changes as three bonded atoms deviate from their preferred bond angles. Deviations increase
energy, helping maintain molecular structure.
3. Torsional Angles: Energy changes due to rotation around a bond. This affects the spatial arrangement of atoms, with certain angles
more stable than others. Modeled using periodic functions.
4. Non-Bonded Interactions: Forces between atoms not directly bonded, including van der Waals (balance of attraction/repulsion) and
electrostatic interactions (attraction/repulsion between charges).
 Force Fields in Molecular
How Force Fields Work Mechanics
In molecular mechanics, the total potential energy V of a system is calculated by summing all the individual
components:

Once the potential energy is defined, molecular mechanics uses numerical methods to minimize this energy. By calculating the potential
energy for different configurations of the atoms, researchers can determine which arrangements are more stable and how the system
behaves under various conditions. The potential energy landscape allows for the identification of local minima (stable configurations) and
transition states (configurations that lead to chemical reactions or conformational changes).

Applications and Benefits

Molecular mechanics, powered by force fields, has vast applications in fields like drug design, material science, and biochemistry. It
allows researchers to simulate molecular dynamics, investigate protein-ligand interactions, and optimize molecular structures
efficiently. Since molecular mechanics operates under classical mechanics, it can handle large systems with thousands of atoms,
making it an invaluable tool in computational chemistry.
Conclusion
Force fields in molecular mechanics provide a practical framework for modeling molecular interactions through classical physics
principles. By encapsulating the complexities of atomic interactions in mathematical functions, force fields enable researchers to
predict molecular behavior, explore conformational spaces, and understand the properties of biological and chemical systems.

Leach, A. R. (2001). Molecular Modelling:

 ONIOM (Our own N-layered Integrated
Molecular Orbital and Molecular Mechanics)
ONIOM is a powerful hybrid computational method that integrates quantum mechanics (QM) with molecular mechanics
(MM) to enable the efficient study of complex systems. This approach is particularly useful in scenarios where certain
parts of a molecular system require detailed quantum treatment, while other regions can be accurately described
using classical mechanics.
Key Concepts of ONIOM
1.Layered Approach: ONIOM divides a molecular system into different layers, each treated with varying levels of theory. The highest
level (often QM) is applied to the most critical part of the system, such as a reactive site, while less critical regions are treated with a
lower level of theory (MM). This stratification allows for efficient calculations without sacrificing accuracy.
2.Effective Potential Energy: The total energy of the system in ONIOM is calculated as a combination of energies from both the QM and
MM layers. The formula can be represented as:

Here, EQM​represents the energy from the quantum mechanically treated layer, EMM​is the energy from the molecular mechanics
layer, and λ is a scaling factor that adjusts the contribution of the MM energy to account for interactions between the layers.
Applications: ONIOM is particularly beneficial in studying enzyme catalysis, where the active site can be treated quantum
mechanically while the surrounding environment can be described using molecular mechanics. It allows researchers to gain insights
into reaction mechanisms, energy barriers, and the effects of solvent or protein environments on chemical reactions.
Conclusion
Overall, ONIOM is a versatile method that enables the detailed analysis of complex molecular systems by combining the strengths of
both quantum and classical approaches, providing an effective tool for researchers in computational chemistry and materials science.

Shin, H., et al. (2015). "ONIOM: A Hybrid Quantum Mechanics/Molecular Mechanics

 Fragment Molecular Method
The Fragment Molecular Orbital (FMO) method is a computational approach designed to make quantum chemical
calculations on large molecular systems more efficient. It works by breaking down a large molecule into smaller,
manageable fragments, and then calculating the properties of each fragment individually. After the calculations for all
the fragments are completed, the results are combined to approximate the behavior of the entire system. This division
into fragments reduces computational cost while still providing accurate electronic structure information for large
systems, such as biomolecules or materials.ately described using classical mechanics.
Key Concepts of Fragment Molecular Method
Fragmentation
In FMO, a molecule is divided into smaller fragments—these can be atoms, groups of atoms, or even sub-molecular units. Each
fragment is treated quantum mechanically, but in isolation. However, the method accounts for interactions between fragments to
ensure that their combined behavior mirrors that of the original molecule. The interactions between fragments can include
electrostatic and exchange-correlation effects, which are essential for maintaining accuracy.
Fragment Energies
Once the fragments are defined, calculations are performed for each one, and inter-fragment interactions are approximated by
computing pairwise interactions between fragments. The total energy of the entire system is then reconstructed by summing the
fragment energies and the energy corrections due to interactions between fragments. This approach ensures that even though
calculations are done on smaller pieces, the overall electronic properties of the system are preserved.
Applications
The FMO method is particularly useful for large molecular systems like proteins, nucleic acids, and materials science applications
where traditional quantum mechanical methods would be too computationally expensive. It's widely used in drug design, enzyme
catalysis, and material properties analysis due to its balance of accuracy and computational efficiency.

WIREs Computational Molecular Science, 2017. "Fragment molecular orbital method:

 Semi-Empirical Methods
What are Semi-Empirical Methods?

• Semi-empirical methods are quantum chemical approaches that use simplifications and
approximations to make calculations more efficient.
• They combine quantum mechanics with empirical data (experimental parameters), reducing the
computational cost by approximating certain integrals.
• These methods are less accurate than ab initio techniques but offer faster calculations for larger
systems.
• They focus on the valence electrons and simplify interactions by neglecting core electrons or
approximating their effects.
Why Use Semi-Empirical Methods?

• They provide a balance between computational efficiency and reasonable accuracy.

• Suitable for studying large molecules or systems where detailed precision isn't crucial.
• Commonly used in organic chemistry, drug design, and molecular biology.
 Types of Semi Empirical Methods
Hückel Method
One of the simplest semi-empirical methods, focused on π-electrons in conjugated systems like benzene.
Assumes constant interaction between neighboring atoms, primarily used in molecular orbital theory to predict
molecular stability and reactivity in aromatic compounds.
Extended Hückel Method
An extension of the Hückel method that includes σ-electrons and a broader range of atoms. Used to calculate
approximate molecular orbitals and qualitative electronic properties of larger systems, though not very accurate
for bond energies.
MNDO (Modified Neglect of Diatomic Overlap)
The first widely adopted semi-empirical method, used for molecular geometry and thermochemistry. Simplifies
overlap integrals between atoms, making it efficient for studying small molecules.
AM1 (Austin Model 1)
An improvement over MNDO, with better treatment of hydrogen bonding and organic molecules. Provides more
accurate bond lengths and energy predictions.
PM3 (Parametric Method 3)
Further developed from AM1, with recalibrated parameters for a wider variety of elements. Commonly used for
studying organic and biological molecules, especially in computational chemistry.
ZINDO (Zerner’s Intermediate Neglect of Differential Overlap)
Specialized for excited-state calculations, including UV/Vis spectra and transition metal complexes. Often used in
photochemistry and coordination chemistry for predicting electronic transitions.
 Materials for Renewable Energy
• Objective: Study the electronic properties of materials used in solar cells or batteries to optimize their
efficiency.
• Explanation:
⚬ Renewable energy materials like silicon, perovskites, or transition metal oxides are crucial in devices such
as solar cells and batteries.
⚬ Using DFT, you can investigate the band structure, charge transport mechanisms, and electronic
properties of these materials to understand how they influence energy conversion and storage efficiency.
⚬ For solar cells, DFT can help in determining the optimal bandgap and charge carrier mobility, essential for
maximizing light absorption and conversion of sunlight into electricity.
⚬ In batteries, DFT can be used to study ion diffusion mechanisms, electrode materials, and potential energy
surfaces to improve battery life and efficiency.
Applications:
• Optimizing perovskite materials for higher solar cell efficiency and stability.
• Designing novel battery materials with better energy storage capabilities and faster ion diffusion.
 Materials for Renewable Energy with Avogadro and
GAMESS
Choosing the Material:
For renewable energy applications, materials such as silicon or perovskites are ideal for studying in solar cells or battery technologies.
You can download structures like silicon from the Materials Project (as we discussed before), or you can import perovskite structures
from sources like the Crystallography Open Database.
Import the material's structure (in .CIF format) into Avogadro for visualization and further manipulation.
Building/Modifying Structures in Avogadro:
Avogadro allows you to modify the surface or bulk structure of these materials, which is important for studying how they behave
under different conditions.
For example, in solar cells, you might be interested in the interface between two materials (e.g., silicon and perovskite). You can
manually construct this interface in Avogadro by aligning and combining the two structures.
Geometry Optimization in Avogadro:
use Avogadro to perform a preliminary geometry optimization using built-in force fields. This provides a reasonable structure for
further DFT analysis.
Setting up the DFT Calculation in GAMESS:
Export the structure from Avogadro as a GAMESS input file and select the DFT functional and basis set appropriate for materials like
silicon or perovskites. For large periodic systems, consider using a pseudopotential for core electrons to save computational cost.
In renewable energy research, you’re often looking at properties like bandgap and charge carrier mobility. DFT in GAMESS will allow
you to calculate the electronic band structure, giving insights into how efficiently the material absorbs sunlight or stores electrical
energy.
Analysis of Results:
GAMESS will provide electronic structure information such as density of states (DOS) and band structure, which are crucial for
understanding a material's performance in solar cells.
Thank
you!