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7 - Quantum Mechanic

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2 views

7 - Quantum Mechanic

Uploaded by

AMANDA PUTRI
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Methods

Molecular Mechanic Quantum Mechanic


¤ Treat molecule as a ball collections ¤ Treat molecule as a system of
held together by springs nuclei and electrons
¤ Electrons are not explicitly ¤ Electrons are explicitly
included included
¤ Fast calculation ¤ Time consuming
¤ Computational requirements do ¤ Computational requirements
not grow fast with the size of growth rapidly with the size of
system system

REVIEW
Quantum mechanic is superior to molecular mechanic
in case of :

- Modeling system with metal atoms


- High accuracy
- Analyze reaction mechanism / covalent bond
formation or breaking
- Prediction spectroscopy’s spectra that involve
electrons (example : UV spectra)
- Prediction of HOMO-LUMO energy

ADVANTAGES OF QM
Reaction Mechanism
Prediction of HOMO-LUMO
Molecular Mechanic (MM)
The form of mathematical expression for the energy and the
parameter in it, constitute a forcefield.
(check MM slide in the previous lecture)

Quantum Mechanic (QM)


The correct mathematical description of the behavior of
electrons in atoms and molecules.

The core of QM method  Schrödinger equation

The QM methods are oriented toward the molecular orbital


(MO) approach.

COMPARISON MM-QM
Schrödinger Equation
is a wave equation involving the kinetic energy of the
electrons and Coulombic interaction between electrons and
nuclei.

The kinetic energy of the nuclei is treated separately  Born-


Oppenheimer approximation

Simplified the Schrödinger equation


without losing the accuracy

Schrödinger Equation
Schrödinger Equation
= Hamiltonian operator
= wave function
= energy

Hamiltonian for Born-Oppenheimer approx.

Schrödinger Equation - 2
Geometry Optimization

Search the solution of Schrödinger equation

Fact :
Only Schrödinger equation for 1 hydrogen was
solved exactly

OTHERS ?? APPROXIMATION

Schrödinger Equation - 3
Pauli
exclusion
principle

ATOMIC ORBITALS – 1
Heisenberg’s uncertainty principle  don’t know exact position
and energy of electron
Density plot

ATOMIC ORBITALS – 2
MOLECULAR ORBITALS – 1
MOLECULAR ORBITALS – 2
MOLECULAR ORBITALS – 3
MOLECULAR ORBITALS – 4
MOLECULAR ORBITALS – 4
N has 7 electrons

Why N2 has triple bond in the stable state, it


can be explained by MO diagram !
BREAKING BOND
HETERONUCLEAR DIATOMICS
FACTORS AFFECTING DEGREE OF ORBITAL
INTERACTION
Semi empirical method  quantum mechanic method

replace the most time consuming parts of those calculations


with values parameterized from experimental results.

Short running time compare to other quantum mechanic methods

Loss some accuracy

Semiempiric Method
Ab initio method  quantum mechanic method

does not rely on calibration against measured


chemical parameters

From the first principle


(ab initio calculations give results in terms of fundamental physical constants –
Planck’s constant, the speed of light, the charge of the electron)

The simplest kind of ab initio calculation is a Hartree-Fock calculation

Ab Initio Method
Semiempiric and ab initio method  based on wave function

DFT = Density Fuctional Theory

DFT
Based not on the wavefunction, but rather on
the electron probability density function or electron density
function, commonly called simply the electron density or charge
density

DFT method  more accurate than semiempiric and ab initio

Semiempiric, Ab Initio, and DFT Method

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