Name: Tan Yi Jie ` Matric ID: SC14041

BSP 3452 Advanced Material Laboratory

Experiment 3: Size Optical Properties Correlation Study in CdSe Quantum Dots
(QDs) using Density Functional Theory Calculations

Executive Summary

The title of this experiment is the size optical properties correlation study in
CdSe Quantum Dots (QDs) using density functional theory calculations. The hypothesis
of this experiment is to prove whether the larger the size of CdSe, the smaller the energy
of band gap. Another hypothesis of this experiment is to determine whether the smaller
the size of CdSe, the colour will change from red to those which contains shorter
wavelength. Besides, are the bulk and quantum dots have difference influences on the
properties of the same material such as CdSe? Does the realistic cluster model of CdSe
QDs is realistic if it is a positive frequency? The objective of this experiment is to
simulate the realistic cluster of CdSe QDs using density functional theory (DFT)
calculations. This experiment also aims to evaluate a realistic cluster model using
harmonic frequency calculations. Furthermore, calculate the energy level of the
conduction band, valence band, and band gap of the simulated cluster is also one of the
objectives of this experiment. The excitation process in bulk semiconductor involves
conduction band and valence band. When a bulk semiconductor absorbs sufficient energy
which is larger and equal to the bulk energy of band gap, the electron will excite to the
conduction band and leave a hole in the valence band. In a QDs semiconductor, the
excitation process involves Highest Occupied Molecular Orbital (HOMO) and Lowest
Unoccupied Molecular Orbital (LUMO). When a QDs semiconductor absorbs sufficient
energy which is larger and equal to the QDs energy of band gap, the electron will excite
to the LUMO and leave a hole in the HOMO. The changes upon size reduction for both
bulk semiconductor and QDs semiconductor can be observed. For the bulk
semiconductor, the energy level of the conduction band and valence band considers very
densely. Hence, the band gap of a bulk semiconductor is small whereas for the QDs
semiconductor, energy level between LUMO and HOMO is very wide. Thus, the band
gap of QDs semiconductor between LUMO and HOMO is larger than the band gap of
bulk semiconductor between the conduction band and valence band. This phenomenon
can be explained by the Quantum Confinement Effect. Due to the restriction movement
of electron, band gap between LUMO and HOMO becomes wider, the colour change can
be observed from dark to bright. In addition, we can notice the changes in energy level,
optical properties and electric properties. The methodology for this experiment is divided
into several parts. First and foremost, realistic cluster model evaluations is started by
using internet browser. After that, DFT calculations includes optimization of a model is
done by using the same software. The procedure is followed by DFT calculations which
include harmonic frequency calculations by applying Gaussview 5.0 software. DFT
calculations which include energy calculations is then done by opening Gaussian 09W
software follows by LUMO density mapping. This experiment continues with realistic
cluster model evaluations, estimation of energy levels of the conduction band, valence
band and band gap using Time Dependent Density Functional Theory (TD-DFT)
calculations by using Gaussview 5.0 software. Finally, the volume of cluster model which
used to estimate the size of CdSe QDs is done by using Gaussian 09W software. The
expected result for this experiment is the larger the size of CdSe, the smaller the energy
of band gap. The colour is expected to change from dark to bright when the size of the
CdSe becomes smaller. Bulk and quantum dots are expected to have difference influences
on the properties of the same material which is CdSe. The realistic cluster model of CdSe
QDs is expected to be realistic when it is a positive frequency. All the hypotheses are
accepted.