28 March 2023

Computational Chemistry III

Dr Krishna K. Govender
JOB 4205
[email protected]
Density Functional Theory
• Modern DFT has its roots in the work of Pierre Hohenberg, Walter Kohn and Lu Jeu Sham

• Hohenberg and Kohn showed that a universal functional for the total electronic energy of an atom,
molecule or ion can be determined in terms of the electron density ρ(r)

• They also showed that the total electronic energy and other observable properties are a functional of ρ(r)

• The equation developed by Kohn and Sham made DFT a practical computational tool

• The Kohn-Sham equation is a Schrödinger equation of a fictitious system of noninteracting electrons that
generate the same density as the system of interest

• This allowed Kohn and Sham to more accurately compute each electrons kinetic energy in terms of
Kohn-Sham orbitals in a manner analogous to HF
[1] Kyle A. Baseden and Jesse W. Tye, Introduction to Density Functional Theory: Calculations by Hand on the Helium Atom, J. Chem. Educ., 2014, 91, 2116-2123 2
Density Functional Theory
Etot[ρ] = ET[ρ] + EV[ρ] + EJ[ρ] + EX[ρ] + EC[ρ]

• The electron density can be represented using several types of mathematical functions

• The original DFT calculations were performed using planewave functions as basis sets

• The infinite extent of these functions was ideal for computations on extended structures such as metal
surfaces or crystalline solids

• In general, the optimization of the total electron density, ρ(r), is accomplished by systematic variation of
the linear expansion coefficients, ci, below to obtain the lowest possible total energy
𝑥

ρ 𝑟 = ෍ 𝑐𝑖 χ𝑖 (𝑟 )
𝑖=1

[1] Kyle A. Baseden and Jesse W. Tye, Introduction to Density Functional Theory: Calculations by Hand on the Helium Atom, J. Chem. Educ., 2014, 91, 2116-2123 3
Density Functional Theory
Etot[ρ] = ET[ρ] + EV[ρ] + EJ[ρ] + EX[ρ] + EC[ρ]

• Unfortunately, the exchange and correlation terms are not known and is probably so
complicated that even if it were known it would not be computationally useful

• Hence there are various approximate exchange-correlation functionals

• The hierarchy of DFT exchange-correlation functionals:

• Local density approximation (LDA): Depends only on the local density at a given point (S-VWN)
• Gradient-corrected approximation (GGA): Depends on local density and its gradient (PW91, LYP, B88)
• Meta-GGA: Depends on density, its gradient and its second derivative (M06-L)
• Hybrid DFT: Mixes in Hartree-Fock exchange (B3LYP, M05-2X and M06-2X)

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Density Functional Theory
𝑥

ρ 𝑟 = ෍ 𝑐𝑖 χ𝑖 (𝑟 )
𝑖=1
𝑥

Molecular orbitals (MOs) ψ 𝑟 = ෍ 𝑐𝑖 χ𝑖 (𝑟 ) Atomic orbitals (AOs)

𝑖=1
• Linear combination of atomic orbitals (LCAO)

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Density Functional Theory
• The basis set needs to be able to approximate the actual wave function sufficiently
well to give chemically meaningful results

• It needs a reasonable computational “cost”

• Integrals should be evaluated quickly and accurately

• Choice always involves a balance between accuracy and computational cost

• More accurate methods using larger basis sets will take more time

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Density Functional Theory

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Summary

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Summary
Method Property
Molecular Mechanics 1. “Steric” or Total energy = sum of
various artificial energy
components…not a real
measurable energy
2. Dipole moment
3. Geometry of the lowest energy
conformation
Semi-empirical, Hartree-Fock and 1. HOMO and LUMO energy
Density Functional Theory 2. UV-Vis spectra
3. Acidity and Basicity (proton
affinity)
4. NMR chemical shifts and coupling
constants
5. IR and Raman spectra
6. Geometry of the minimum energy
structure
7. Others

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Summary
Method Advantage Disadvantage
Molecular Mechanics Fast and allows for simulation Parameters may not be
of large molecules available
Cannot model bond making
and bond breaking
Hartree-Fock Results can be quantitative Electron correlation limits
accuracy
Can have high computational
expense for larger systems
Semi-empirical Good qualitative and Parameters may not be
quantitative results available
Inexpensive computational
cost
Density Functional Theory Better accuracy than HF Limited to smaller systems
Computational cost is high for
larger systems

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Summary
• A unit found in computational chemistry software packages for the energy is the
Hartree

• The conversion from Hartree can be achieved by using the following

• 627.51 kcal/mol
• 2625.5 kJ/mol
• 27.211 eV
• 219474.6 cm-1

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Examples
• Molecular geometry:
• The shape of the molecules bond lengths, angles and dihedrals

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Examples
• Energies of molecules and transition states:
• This tells us which isomer is favored at equilibrium and how fast a reaction can go

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Examples
• Chemical reactivity:
• Identifying electrophilic sites and nucleophilic sites and predict where various kinds of
reagents will attack a molecule

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Examples
• IR, UV and NMR spectra:
• These can be calculated, if the molecule is unknown then someone trying to make it knows
what to look for

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Examples
• The interaction of substrate with enzyme:
• See how molecules fit into active sites of an enzyme when designing better drugs

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Examples
• The physical properties of substances:
• The strength and melting point of polymer, this would depend on how well the monomers fit
together and how strong is the force between them

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Examples
• Reactivity
To determine which
is most reactive one
Needs to know what H3C-Br
H3C-F is the energy gap for
each
HOMO
LUMO
Determine the
difference between
the two
H3C-Cl H3C-I
Larger energy
means less reactive
and vice versa

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Examples
• Spontaneity

+ +

H3C-Cl HBr
HCl
H3C-Br

• Optimize each structure • ΔG = G(products) – G(reactants)

• Determine the thermodynamic properties for each
• ΔG = Negative then reaction
• From the thermodynamic properties determine the free energy (G)
spontaneous

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Software
• Spartan
• Gaussian
• Jaguar
• DMol3
• Quantum Espresso
• CASTEP
• ORCA

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THE END

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