1. The importance of clusters was first proposed by the Irish-born chemist Robert Boyle in his 17.
17. Cyclotron frequency measurement can be used to determine the mass-to-charge ratio
book, The Sceptical Chymist.
2. Laser vaporization it is a pulsed cluster source which is used to produce small- and
medium-sized clusters.
3. Pulsed arc cluster ion source they are related to laser vaporization sources but instead of
the laser here, the cluster precursor is vaporized by an intense electrical discharge.
4. Supersonic (Free Jet) Nozzle Sources Supersonic Nozzle Sources are of two main types,
unseeded and seeded. In the first type, clusters of inert gases, molecules and low boiling
metals (e.g Hg) are formed. In the other type, the metal is vaporized (with a vapor pressure of
10-100 mbar) in an oven and the vapor is mixed with (seeded) an inert carrier gas at a
pressure of several atmospheres 105-106 pa) at a temperature of 77-1500K.
5. Gas Aggregation or Smoke Sources the source utilizes the property of aggregation of
atoms in inert media.
6. Knudsen Cell the Knudsen cell produces a continuous, low flux beam of clusters.
7. Liquid Metal Ion Source these sources are primarily used to produce clusters of multiple
charges, with low-melting are used in which a high energy ion beam is used to sputter atoms,
ions and clusters from a surface metals.
8. Sputter Sources Sputtering Sources are used in which a high energy ion beam is used to
sputter atoms, ions and clusters from a surface.
9. Nucleation. The nucleation can be a homogenous or heterogeneous. Heterogeneous implies
the nucleation occurs on foreign objects, dust particles, etc. in it, collision between like or
unlike atoms occurs such that the thermal energy is lower than the binding energy of the
species formed. Dimer formation occurs when the third body involved in the collision removes
the excess internal energy as kinetic energy. The dimer acts as a seed for further
condensation and additional growth occurs.
10. Growth. Initial growth occurs by the aggregation of atoms or molecules one at a time.
Coalescence of clusters results in the formation of larger clusters.
11. The formed clusters can exist as neutrals or ions (both positively and negatively charged).
Various mass spectrometers are used to detect the ionic clusters. The clusters which exist in
solid or in liquid state can be analyzed by several spectroscopic, microscopic or diffraction
techniques.
12. Mass spectrometers are unique devices used to study the exact constitution of the clusters
which exist in the gas phase. From the mass we can easily calculate the empirical formula of
the cluster. Wien filter, time of flight TOF), quadrupole mass filter (QMF), and ion cyclotron
resonance (ICR) are the normal kinds of mass spectrometric techniques used to study
clusters (although magnetic sector instruments can also be used).
13. Wien Filter this is allow resolution (m/m10-2), low mass range(less than m/z 1500)
instrument. Here mass separation is accomplished using crossed homogeneous electric (E)
and magnetic (B fields, perpendicular to the ionized clusters beam which travels along the
axis of the filter.
14. Quadrupole Mass Filter (QMF) it is the most widely used type of mass spectrometers
today because of its ease of use, compactness and low cost. The principle of QMF is based
on the achievement of a stable trajectory for specific ions in a hyperbolic electrostatic field.
15. Time of Flight (TOF) Mass Filter TOF has emerged as an efficient mass analyzer.
16. Ion Cyclotron Resonance (ICR) performs all the mass spectrometric studies in a single cell.
They include mass analysis, ion selection, ion interaction and product ion mass analysis.
Ions are trapped by a combination of a static quadrupole electric field and a highly uniform
magnetic field for strength, B. Due to the magnetic field, ions move at the cyclotron frequency.
(m/z) of the ions.
18. Fourier transform ion cyclotron resonance (FT-ICR) - the ideal technique for cluster mass
spectroscopy due to the superior resolution and possibility of combining with cluster sources
and extreme sensitivity.
19. Clusters can be classified according to both the type atoms of which they are made and
the nature of the bonding in these clusters.
20. Metal clusters are formed form alkali metals, alkaline earth metals and transition metals.
- may be formed from single metallic element or from more than one metal, giving
rise to intermetallic or nanoalloy clusters.
21. Neutral sodium clusters produced in a gas aggregation source. Metallic sodium is heated
in an oven to a temperature of about 400C.
22. Silver, aluminum, copper and nickel clusters - are made from molecular precursors.
23. Silver clusters high aggregation from silver trifluoroacetate can be achieved in matrix
assisted laser desorption ionization (MALDI) conditions using 2-(4-hydroxyphenylazo)
benzoic acid (HABA) as the matrix.
24. Semiconductor clusters - are generated from elements which are semiconductors in nature
such as silicon, carbon and germanium.
25. Carbon cluster has the tendency to form a greater variety of clusters as compared to other
elements.
- The bonding in these clusters is covalent in nature.
- Produced by using an electric discharge between graphite electrodes
- Generated clusters were detected by mass spectrometers
26. Silicon clusters the first reported silicon clusters were generated by laser flash
evaporation, quenched in a carrier gas and then cooled by supersonic expansion.
27. Metcars
These are closed-cage clusters made of metals and carbon.
Mo-C, Ti-C, Hf-C, V-C, Cr-C example of clusters.
28. Ti8C12 the first cluster discovered.
- This discovery has led a number of researchers to investigate analogues clusters.
- These clusters are called as metallocarbohedrenes or met-cars.
29. Rare gas clusters are the earliest clusters detected in molecular beam experiments.
- have fully filled electronic configuration, as a result of which them are inert.
30. Mackay icosohedra outer shells of the icosahedral clusters
31. Lennard-Jones potential model interatomic potential used for magic numbers consistent
with calculations on neutral rare gas clusters.
32. Mercury clusters are generated by a molecular cluster beam source.
33. Monochromatized radiation typically from a synchrotron
-Used to photoionize the neutral cluster beam.
-The light coming out from the undulator, one of the insertion devices in a
synchrotron, used for enhanced light intensity provides more than 10 13
photons/sec/m rad.
34. The surface modification of nanocrystals is important for the following reasons:
It removes surface states, thus making near band gap emission possible. Due to the removal
of defects, the emission becomes narrow.
 It adds chemical versatility to the system allowing it to become part of a larger structure. This
is important in the use of such materials in polymers, inorganic matrices, etc. It is also
important in making the system biocompatible.
Surface passivation and suitable functionalization make the system chemically inert and
thermally stable.
34. Trimethylsilylphosphine is used as the phosphorus precursor. A mixture of TOPO and trioctyl
phosphine (TOP) is used as the colloidal stabilizer.
35. graphite can be understood starting from an assembly of benzene fragments, or diamond can
be thought of as an assembly of tetrahedrally connected sp3 carbon atoms.
36. Absorption and emission spectroscopy are performed to understand the quantum
confinement of the system.
37. Emission is referred to as global emission when the excitation energy is much higher than
the absorption maximum of the sample
38. X-ray diffraction is the principal method used to identify the phases present in a solid state
material
39. TEM most important characterization tool for a nanomaterial, as nothing can be more
convincing than seeing the object.
This can reveal the microscopic structure and atomic composition by using energy dispersive
X-ray.
40. Different techniques used for the characterization of materials:
Thermogravimetry
Differential scanning calorimetry
X-ray photoelectron spectroscopy
Raman spectroscopy
infrared to heating at a constant rate
41. Differential scanning calorimetry can be used for evaluating phase changes in the material.
42. X-ray photoelectron spectroscopy it provides direct information on the electronic structure.
43. If one measures the charge of the particle, Q as a function of the external charge, Q = CU, we
get a step-like function which is called Coulomb Staircase.
44. Citrate reduction method of Turkevitch is the most popular where a solution of the gold or
silver salt (typically 1mM) is boiled with a higher concentration (typically 1M) of sodium citrate
for a few minutes
45. The 3D monolayers or monolayer-protected metal clusters (MPCs) belong to a category of
materials wherein the constituting monolayer-protected clusters or nanoparticles behave like
molecules.
46. UV/vis spectroscopy has been used to characterize the core of the material.
47. High resolution transmission microscopy- showed FCC packing of atoms in the gold core with
a mixture of particle shapes with predominantly truncated octahedral, cuboctahedral and
icosahedral structures at lattice resolution on size-selected gold nanocrystallites.
48. X-ray photoelctron spectroscopy- used to find out the oxidation state of gold in the material.
49. IR spectroscopy- a powerful tool used to study the structure of the adsorbate on the metal
surface.
50. 13C NMR spectra of alkaline thiol- stabilized clusters for three different alkyl chain lengths
showed that the peak narrows down as the distance of the carbon from gold surface
increases.
51. Superlattice is a periodic, synthetic multi-layer, wherein a unit cell, consisting of successive
layers that are chemically different from their adjacent neighbors, is repeated.
52. Monodispersity is another important factor that controls the formation of superlattice. Size
selective separation is requiredto make monodisperse particles. The method developed by
Murray, et al., 1993, facilitates the synthesis of monodisperse particles.
53. Method by Murray, et al., 1993- metal-organic precursors are injected into a hot solution
containing co-ordinating ligands like trioctyl phosphine.
54. The term used to describe the synthesis of core-shell partcles with well-defined morphologies
and tailored properties is called particle engineering. This is achieved by encapsulating the
nanometal core with the shell material. The shell protection imparts certain functional
properties to the nanomaterial including: (1) monosdispersity in size (2) core and shell
processibility, (3) solubility and stability, (4) ease of self-assembly, and (5) applications in
nanoscale optic, nanoelectonics, as well as in magnetic, catalytic, chemical and biological
fields. Shell protection is absolutely necessary for the following important reasons: (a) the
shell can alter the surface charge, reactivity and functionality of the metal core thereby
enhancing the stability and dispersibility of colloidal materials : (b) by choosing a suitable
shell-forming material, we can incorporate magnetic, optical and catalytic properties into the
composite material; (c) encasing the metal core in a shell invariably protects it from physical
and chemical changes; and (d) core-shells exhibit improved physical and chemical
characteristics as compared to their single component counterparts.
55. Nanosized metal clusters have intense colour, which can be tuned by varying the size of the
clusters.
56. The methodology uses 3-aminopropyl trimethoxy silane (APS), the silane coupling agent,
which can bind to the nanoparticles surface and can also function as an anchor point for the
chemical deposition of active silica (Sio32-).
57. Faradays Gold. A sample flask containing a sample of a gold colloid made by Michael
Faraday in 1857. A gold colloid is a suspension of microscopic particles of metallic gold in
water. He used phosphorus to reduce a solution of gold chloride, as the metal precipitates out
it forms particles of the order 100 nanometres in diameter. The colour of the colloid is
determined by the particle size.
58. Lycurgus Cup. The glass chalice, known as the Lycurgus Cup because it bears a scene
involving King Lycurgus of Thrace, appears jade green when lit from the front but blood-red
when lit from behind
59. Quantum Corral. In 1993 D. Eigler and his collaborators created a so-called "quantum corral"
by placing 48 iron atoms in a circle on a copper surface and thus demonstrated a shining
example of forming nano-objects through the manipulation of individual atoms with the use of
scanning tunnelling microscopy (STM).
60. Since Raman spectroscopy is a nondestructive method, it is commonly used in
characterization of the structure and quality of synthesized diamond films
61. Henglein synthesized core-shell alloys of Au-Pt through the simultaneous reduction of
chloroauric acid and chloroplatinic acid.
62. Semiconductor nanocrystal exhibit interesting size-dependent optical properties because of
the confinement of electronic wavefunctions.
63. . The synthetic methodologies adopted for polymer capping of nanoparticles are of two main
classes, namely: (a) polymerization at the nanoparticle surface, (b) adsorption of pre-formed
polymer onto the nanoparticle cores.
64. Power X-ray diffraction is one of the powerful techniques for the characterization of core-shell
nanoparticles.
65. Optical spectroscopy is another very important tool used for the characterization of
nanomaterials.
66. Plasmons-electromagnetic resonance resulting from the collective oscillations of conduction
band electrons.
67. The resonance frequency mainly depends on the restoring force.
68. Zeta potential or electrokinetic potential is the potential at which the fixed part of the double
layer along with a part of the mobile layer moves towards an electrode.
69. The greater the zeta potential, the greater will be the stability.
70. Zeta potential depends on a number of parameters like:
Surface charges
Ions adsorbed at the interfaces
Nature and composition of the surrounding medium
71. The porosity of core-shell nanoparticles was extensively investigated by using cyclic
voltammetry and absorption spectroscopy.
72. The optical interaction induces a dipole moment that oscillates coherently at the frequency of
the incident wave.
The frequency of this oscillation depends on the:
Electron density
Effective mass
Shape and size of the charge undergoing oscillation
73. The collective oscillation of the free conduction electrons is called plasmon resonance
74. The dipole plasmon frequency is related to the dielectric constant of the metal.
75. Organic non-linear optical materials can be used for high density data storage, phase
conjugation, holography, and spatial light modulation.
76. Among the non-linear optical applications, optical limiting has been the most promising.
77. Magnetic core-shell particles are used in clinical applications and biotechnology, as the shells
can be made biocompatible.
78. The magnetism of core-shell nanoparticles can be tuned by varying the shell thickness
79. The Fe58Pt42/Fe3O4 core shell nanoparticles are ferromagnetic at low temp but super-
paramagnetic at room temperature.
Magnetic nanoparticles are used in various areas such as:
Bearings
Seals
Lubricants
80. Magnetic nanoparticles are being tested as contrast-enhancing agents for cancer imaging
and therapy.
81. Catalysis by core-shell nanoparticles is a very important, active and emerging area, which
can have a tremendous impact in the chemical industry, pharmaceutical products and the fuel
sector.
82. Two-step synthesis. The first step is to synthesis of the core-shell particles. Silver
nanoclusters are made first as in the case of monolayer protected clusters. The monolayer
made has a carboxyl functionality. The method used is called the Brust method.
83. Fluorescein Isothiocyante@SiO2
Self-quenching occurs due to decrease in the quantum yield of the encapsulated dye.
84. Transmission Electron Microscopy
It is main technique used for the characterization of nanoshells as can see the nano
structures.
85. Fluorescence Spectroscopy
Used to characterize nanoshells
Emission spectrum of the incorporated molecule can be used for characterization
86. Cyclic Voltammetry
Provide valuable information on the molecules present inside the nanoshell, thus probing the
shell indirectly
Used in looking for the reactions taking place inside the nanoshell
87. Infrared Spectrocopy
Provides information about the kind of linkages present in nanoshells