ELECTRON

Department of ECE, Amrita Vishwa Vidyapeetham, Coimbatore

Characterizing properties of gold nanoparticles by

molecular modeling and simulation techniques
Rajasree P.M#1, Krishnan Namboori P.K.*2
#

Department of Electronics and Communication Engineering ( Bio-Medical Engineering)

** Computational engineering and Networking,
School of Engineering, Amrita Vishwa Vidyapeetham University,
Ettimadai, Coimbatore-641 105
1

rajasree.pm@gmail.com
n_krishnan@ettimadai.amrita.edu

Abstract It has become high time to find an effective

solution to cancer treatment. Gold nanoparticles which show
unique optical ,electronics and biomedical properties can be
used for many pharmaceutical and diagnostic applications.
Properties of nanoparticles change with the dimension. A
purely experimental analysis of quantum dot would be highly
impractical. The only alternative for this is to design a
completely theoretical modeling and simulation useful in
characterizing properties. In this work quantum mechanical
modeling and molecular dynamic simulation of 0.6nm size
gold nanoparticles has been carried out to identify the
properties generated by these designing techniques.
Keywords gold nanoparticles, quantum mechanical modeling,
molecular dynamic simulation, DFT, Quantum dot.

I. INTRODUCTION
The biochemical applications of nano particles are a
long awaited advance towards the battle of a number of
diseases including cancer which raises new possibilities in
the diagnostic and treatment areas. Particles with
dimensions in the order of a billionth of a meter are known
as nanoparticles. Nanoparticles allow unique interaction
with biological systems at molecular level. They have been
mainly used to improve the delivery of therapeutic agents
to the cancer cells with the goal of minimizing toxic effects
on healthy tissues while maintaining anti tumour efficacy.
Gold (Au) nanoparticles have optical, electronic,
catalytic, biocompatible properties and a potentially high
surface reactivity. Hence gold nanoparticles have been
widely used in the direction of detection, diagnosis and
treatment of various types of cancers. Gold is known to be
a good electrical and thermal conductor, and it is relatively
easy for these particles to bind with antibodies,
carbohydrates, and other pharmacologic agents. Moreover,
gold has been used for many years in the treatment of
rheumatoid arthritis, and is free from any cytotoxic effects.
When excited with an electromagnetic field,
nanoparticles produce an intense absorption attributed to
the collective oscillation of electrons on the particle
surface, termed a Plasmon resonance. The resonant
frequency is highly dependent on particle size, shape,
material, and environment. By altering these characteristics,
the frequency can be shifted over a wide range of
wavelengths, making nanoparticles into functional
materials for many applications.

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It has been reported that gold nanoparticles of

dimensionality 5nm convert allowed radiofrequency into
high frequency [1]. The unique property of converting
allowed radiofrequency into high frequency is known as
Quantum Dot property and could be used for destroying
cancer cells. Actually the technique involves placing gold
quantum dot of the required size into cancer cells- either
directly or with the help of some carriers. The
dimensionality of gold nanoparticles determines the
frequency of radiation produced from it on passing
radiofrequency. Moreover mechano-chemical properties
are equally important in deciding most of the biochemical
properties. In this work, a designing strategy for gold
nanoparticles to excavate mechano-chemical properties has
been made. The modeling has been done by the quantum
mechanical method in the Density Functional Theory
(DFT) level of computation. Mechanical properties like
Bulk Modulus, Shear Modulus and Compressibility have
been computed by molecular dynamic simulation
technique.
II. PRINCIPLE
DFT level of computation has been identified as most
suitable for nanoparticles [2]. The main idea of DFT is to
describe an interacting system of fermions via its density
and not via its many-body wave function. For N electrons
in a solid, which obey the Pauli principle and repulse each
other via the Coulomb potential, this means that the basic
variable of the system depends only on three the spatial
coordinates x, y, and z rather than 3*N degrees of freedom.
DFT in principle gives a good description of ground state
properties, practical applications of DFT are based on
approximations for the so-called exchange-correlation
potential. The exchange-correlation potential describes the
effects of the Pauli principle and the Coulomb potential
beyond a pure electrostatic interaction of the electrons.
A common approximation is the so-called local density
approximation (LDA) which locally substitutes the
exchange-correlation energy density of an inhomogeneous
system by that of an electron gas evaluated at the local
density. While many ground state properties (lattice
constants, bulk moduli, etc.) are well described in the LDA,
the dielectric constant is overestimated by 10-40% in LDA
compared to experiment. This overestimation stems from

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ELECTRON
Department of ECE, Amrita Vishwa Vidyapeetham, Coimbatore
the neglect of a polarization-dependent exchange
correlation field in LDA compared to DFT.
The electronic energy has been expressed as a sum of
the kinetic energy
potentials

[Vn ] ,

[Ts ]

, energy due to external

Coulomb energy

[Vc ]

and exchange-

correlation energy Exc as given in Equation 1.

E ( ) = [Ts ] + [Vn ] + [Vc ] + E xc

(1)

The energy due to external potentials can be written as,

[Vn ]= V n (1)(1)d1

(2)

The most common external potential for the electronic

system in a molecule is the nuclear attraction potential:

ZA
|
R
A r1|
A

Vn =

(3)

The external potential could also include external magnetic

or electric fields. The Coulomb energy can be written as:

1 (1) (2)
(4)
d d
|r1 r2 | 1 2
The Kohn-Sham theory [3] provides a method
applicable to determine the electronic density by solving a
model problem in which the electrons are not interacting.
This method can in principle provide the exact density for
the system of interest. In this formalism the electronic
density is expressed as the density due to a determinantal
wavefunctions.

[Vc ]= 2

occ

= i* i

(5)

h i = 2 + Vn + Vc + Vxc i = i i
2

(6)

i =1
Further, a model Hamiltonian is formulated for the noninteracting reference system, which yields a set of self
consistent differential equations, called Kohn-Sham
equations:

where the first term in the Hamiltonian is the kinetic

energy operator, the second term is defined in
Equation.3.The Coulomb potential can be defined as :

Vc =

(2)

| r1 r2 | d 2

E xc

Table 1 Mechanical properties

(8)

The exchange-correlation energy term contains all

contributions not considered in the first three terms,

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III. PRESENT WORK

Molecular modeling has been done in the DFT level by
using abinit tool of nanoHUB [7,8,9]. The nuclear-nuclear
interaction Ewald energy, correlation energy are found to
be respectively -38685.54 eV and -20255.36 eV. Highest
occupied molecular orbital (HOMO), lowest unoccupied
molecular orbital (LUMO) energy gap has been computed
as 5733.03 eV. Total energy of the system is found to be
-59582.30 eV.
Molecular dynamic simulation has been carried out with
General utility Lattice Program (GULP) [10]. Potential
energy, bulk modulus, shear modulus and compressibility
of the nanoparticles have been computed (Table 1 and
Table 2).

(7)

The exchange-correlation potential is defined as

the functional derivative of the exchange-correlation
energy, with respect to the electronic density.

V xc =

including the difference in the kinetic energy of the

interacting and non-interacting systems in the Kohn-Sham
formalism. The exact dependence of the exchangecorrelation energy on the electronic density is not known,
however various levels of approximations exist to calculate
this term.
The simplest approximation of the exchangecorrelation term is used in the Hartree-Fock-Slater method,
which includes only the exchange term of the
homogeneous electron gas. The local density
approximation (LDA) methods take not only the exchange,
but also the correlation term for the homogeneous electron
gas to approximate EXC. Of particular importance is the
local exchange-correlation potential suggested by Vosko,
Wilk, and Nusair [4], which we have used in our studies .
Generalized gradient (GGA) corrections to the VoskoWilk- Nusair local density (LDA) exchange-correlation
energy has been carried out in this work using the BLYP
[5] functional. This functional is obtained by adding
gradient corrections to the LDA method - specifically the
exchange correction of Becke and the correlation function
of Lee, Yang and Parr.
In molecular dynamics simulation, a proper geometry
optimization will be carried out. This removes any strong
Vander Waals interactions that may exist, which might
otherwise lead to local structural distortion and result in an
unstable simulation. The energy computation is made by
following Newtonian mechanics [6]. Thus by knowing the
initial positions of all atoms it is possible to find the future
positions and velocities of all atoms by integrating the
classical equations of motion. The interactional forces
between particles depend on only positions and not on
particle velocities. So we can write force as a gradient of
potential.

Reuss

Voigt

Hill

(GPa)

267.46578

267.487339

267.47659

Shear

81.76929

97.38158

89.57539

Bulk Modulus

Modulus(GPa)

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Department of ECE, Amrita Vishwa Vidyapeetham, Coimbatore

Compressibility(1/GPa) factor is found to be 0.00373889.

Table 2 Energy computation by MD

Properties
Kinetic Energy
(eV)
Potential
Energy(eV)
Total Energy(eV)
Temperature (K)

Instantaneous
2.094728

Averaged
2.091339

-201.452323

-201.175151

-199.357603
300.101138

weakly interacted in the solid phase. Computed Bulk

modulus and shear modulus values imply low rigidity of
the particle. The surface is found to be weakly hydrophilic
suggesting low solubility of the particle in water.
REFERENCES
[1]

-199.883813
299.616713

The nanocrystal gold of 0.6nm dimension assumes almost

spherical shape with 55 atoms. The surface area of the
system in 100 and 111 space lattice has been computed as
198.78 and 114.76 A2
IV. CONCLUSION
The surface area computation is a very important step in
biochemical property prediction with the help of steric
descriptors. Surface electron density has been computed
(Fig 1), which clearly indicates the possibility for Van der
Waal,s interactions. Very low energy values suggest the
particle to be

[2]

[3]

[4]
[5]
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Figure 1. Electron density of 0.6 nm gold

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