Advanced analysis method for energy material

[1] Explain Bragg's law using schematic diagram and mathematical equation.

On the previous diagram, the “reflected” rays combine to form a diffracted beam if they differ

in phase by a whole number of wavelengths, that is, if the path difference AB-AD = n where

n is an integer (order of diffraction). Therefore

[2] Explain what kind of information is available from X-ray diffraction (XRD) and how to

use them for the research.

Information:
  X-ray crystallography relies on the dual wave/particle nature of x-rays to discover
information about the structure of crystalline materials.
 X-ray fluorescence spectrometry relies on characteristic secondary radiation emitted
by materials when excited by a high energy x-ray source and is used primarily to
determine amounts of particular elements in materials.
 X-ray radiography is used for creating images of light-opaque materials relies on the
relationship between density of materials and absorption of x-rays. Applications
include a variety of medical and industrial applications.
Uses:
 Identification of single-phase materials – minerals, chemical compounds or other
engineered materials.
 Identification of multiple phases in microcrystalline mixtures (i.e., rocks).
 Determination of crystal structure of identified materials.
 Recognition of amorphous materials in partially crystalline mixtures.
 Methods for identification and structural analysis of clay minerals.

[3] If your sample contains a lot of nanoparticle but don't know the size, then describe

the method for the determination of particle using XRD.

X-ray Powder Diffraction: Obtain the values from a table for the wavelength used by XRD

machine.

1) Pick the largest peak and look in the appropriate section of the search manual

2) Pick the second peak, look in the first several columns of section for a match.

3) Once you have found a decent match for two peaks, check for other peaks.

4) Relative intensity of peaks is given in the subscript and provides an approximate guide-

rarely are they exactly a match in real life.

5) Use your knowledge.

6) Eliminate other possibilities by using additional peaks.

7) For more detail, go to Power Diffraction File catalogs cards.

[4] The following is the list of the keyword often appeared in the research paper. Describe

briefly it.
Lattice: Crystalline solids consist of regular arrays of atoms, ion, or molecules with interatomic

spacing on the order of 100 pm or 1 A.

Reciprocal Space: The reciprocal lattice exists in reciprocal space (also known as momentum

space or less commonly as K-space). The reciprocal lattice represents the Fourier transform of

direct lattice.

Real Space: Direct lattice is usually a periodic spatial function in real-space and is what one

would commonly understand as a physical lattice.

ICSD: Inorganic Crystal Structure Data Base is for fully identified inorganic crystal structures.

PDF: Power Diffraction File contains over 300,000 diffraction patterns. Modern computer

programs can help you determine what phases are present in sample by quickly comparing

diffraction data to all of the patterns in the database.

ICCD: International Center of Diffraction Data

[5] Compare the powder diffraction method with the single crystal diffraction method.
 Powder Diffraction

Powder diffraction Single crystal diffraction

Unlike single-crystal XRD, powder XRD looks at a Single-crystal XRD allows for absolute
large sample of polycrystalline material and structure determination. With single-
therefore is considered a bulk characterization crystal XRD data, the exact atomic
technique. The powder pattern is considered a positions can be observed, and thus
"fingerprint" for a given material; it provides bond lengths and angles can be
information about the phase (polymorph) and determined. This technique provides the
crystallinity of the material. Typically, powder structure within a single crystal, which
XRD is used to study minerals, zeolites, metal- does not necessarily represent the bulk
organic frameworks (MOFs), and other extended of the material. Therefore, additional
solids. Powder XRD can also be used to establish bulk characterization methods must be
bulk purity of molecular species. utilized to prove the identity and purity
of a compound.
All the symmetry-equivalent reflections have the When the space-group symmetry is
same d spacing with the result that individual unknown, reflections can be measured
intensities cannot be measured. and compared with other possible
symmetry equivalent reflections.
The three-dimensional data are “compressed” The information is distributed in three-
into one-dimension. dimensional space.
Although structure determination by powder X- For structures with less than 100 atoms
ray diffraction may not be as accurate as that by in the asymmetric unit, single-crystal
single-crystal X-ray diffraction, improvements will techniques are always guaranteed to be
likely be achieved through future advancements successful with accurate parameters of
in instrumentation and algorithm development. cell dimensions.
[6] Define the following Rietveld method related keyword and describe it.

R values indicate the agreement between observed and calculated quantities.

Rwp: Weighted profile R-factor, follows directly from the square root of the quantity minimized,

   
2 2
scaled by the weighted intensities 𝑤𝑖 : R 2   w y C,i  y O,i /  w y O,i
wp i i
i i

RB: R-Bragg R  I
B
K
O,K
 I C , K /  I O, K . IK is the intensity of Bragg K reflection at the end
K

of each cycle of refinement.

RF: Structure R-factor R  I  I C ,K /  I O,K

1/ 2 1/ 2 1/ 2
F O,K
K K

RP: R Profile R  y
p
i
O ,i
 y C ,i
/ y
i
O ,i

Fractional Coordinate: are expressed as fractions of the unit cell in each of the three directions

a, b, c separated by the angles α, β, γ.

Profile Parameter: the parameters of the diffraction profile. The parameters specific to each

phase, which vary during the refinement are structural and non-structural (parameters of the

half width (U, V, W), asymmetry, 2θ zero, preferred orientation and coefficients of the

background radiation.
[7] Define the structural parameters in Rietveld method and describe it briefly.

Atomic positions: Crystal structure is considered known when atom positions are known very

precisely. The amplitude of light scattered by a crystal is determined by the arrangement of

atoms in the diffracting planes. X-ray diffraction intensities ––> atom positions.

Unit cell parameters: Indexing the XRD pattern, a [Å], b [Å], c [Å], β [˚], V [Å3]. The diffraction

peak position is a product of the atomic bond distances in the crystal. X-ray diffraction

reflection positions ––> cell size, space group symmetry.

Structure factor: (Fkhl) quantifies the amplitude of light scattered by a crystal 𝐹𝑘ℎ𝑙 =

𝑗=1 𝑁𝑗 𝑓𝑗 𝑒𝑥𝑝[2𝜋𝑖(ℎ𝑥𝑗 + 𝑘𝑦𝑗 + 𝑙𝑧𝑗 )]. Fhkl sums the result of scattering from all of the atoms in
∑𝑚

the unit cell to form a diffraction peak from the (hkl) planes of atoms.

Scattering factor: (fj) quantifies the efficiency of scattering from a group of electrons in an

atom. The number of electrons around an atom defines how strongly it will scatter the incident

X-ray beam.

Occupancy factors: (sof) indicates what fraction of a site is occupied by a specific atom. The

sof is Nj in the structure factor equation. sof = 1, every equivalent position for xyz is occupied

by a specific atom. sof < 1, some of the sites are vacant.

Wyckoff Site notation: it is a shortcut to indicate the type of site that the atoms occupy in

the crystal, and if x, y or z can be changed or they must be fixed to preserve the symmetry

of the crystal.

Thermal vibration parameters (isotropic and anisotropic): Thermal motion of the atom

changes the scattering factor. The amount of vibration is quantified by the Debye-Waller

temperature factor.

[8] Why you need the quantitative method using X-ray diffraction?

Quantitative analysis of diffraction data usually refers to the determination of amounts of

different phases in multi-phase samples. Quantitative analysis may also be thought of in

terms of the determination of particular characteristics of single phases including precise

determination of crystal structure or crystallite size and shape, with quantifiable numerical

precision from the experimental data itself. Though “standard” patterns and structural data

are used as a starting point, the most successful quantitative analysis usually involves modeling

the diffraction pattern such that the calculated pattern(s) duplicates the experimental one.

[9] Explain the following quantitative analysis method.

Single line method: The procedure consists in measurements of a given peak intensity for a

sample and for the standard. There are many methods, which utilize single-line intensities for

the Quantitative Phase Analysis (QPA), and these methods can be classified into one category,

which may be called the single-line QPA method.

Multi line method: This method uses several lines per element in diffraction spectra for

calculations, and high accurate and precise concentration per element can be obtained.

Measurement uses sensitivity factor for a given type of the spectrometer.

Whole pattern decomposition method: Whole-powder-pattern decomposition (WPPD)

methods simultaneously refine the unit-cell parameters and extract the best estimations of

the Bragg peak intensities from a complete diffractogram. Methods in this category are based

on the whole-powder-pattern fitting (WPPF).

[10] Compare the strong and weak points of the Single line method, Multi line method

and Whole pattern decomposition method

Single Line Multi Line WPPD

Strength  Intensity ratio  Does not require  Standardless

𝐼𝑢𝑛𝑘𝑛𝑜𝑤𝑛 ⁄𝐼𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 standards, it analysis with high
of one or more
considers the precision based
reflections.
instrumental and on assumption
  No need of matrix effects and that entire sample
structural it derives is crystalline.
information. quantitative  Minimization of
information from systematic errors
statistical analysis (e.g. due to peak
of all overlap.
photoelectron  Preferential
intensities visible Orientation (PO)
in the spectra. can be modeled.
 Provide reliable  Accuracy close to
results of X-Ray
quantitative fluorescence
analysis elemental analysis,
with the
advantage of
being sensitive to
structural
differences 
direct QPA of
polymorphs.
Weakness  Strongly affected  Selection of an  It generally
by any aberrations adequate line can returns relative
in data originating be challenging abundances and
from sample with line-rich limited to well-
preparation, data matrices, which defined crystalline
collection regime means that species.
or the sample. selecting several  Its accuracy is
 Need ad-hoc lines per element difficult to
mixtures for would be even determine.
calibration curves more complex.
itself.
[11] Please explain the following analysis software that can be found in

http://www.ccp14.ac.uk/.

Fullprof: program has been mainly developed for Rietveld analysis (structure profile

refinement) of neutron (constant wavelength, time of flight, nuclear and magnetic scattering)

or X-ray powder diffraction data collected at constant or variable step in scattering angle

2theta. The program can be also used as a Profile Matching (or pattern decomposition using

Le Bail method) tool, without the knowledge of the structure. Single crystal refinement can

also be performed alone or in combination with powder data. Time of flight (TOF) neutron

data analysis is also available. Energy dispersive X-ray data can also be treated but only for

profile matching.

GSAS: is a set of programs for the processing and analysis of both single crystal and powder

diffraction data obtained with x-rays or neutrons. It is capable of handling all of these types

of data simultaneously for a given structural problem. In addition, it can handle powder

diffraction data from a mixture of phases refining structural parameters for each phase. GSAS

is designed to be easy to use and features a menu driven editor (EXPEDT) equipped with help

listings and error trapping features. EXPEDT is used to prepare all input for the main calculation

programs in GSAS. The entire GSAS system is written in FORTRAN and uses some system

callable features.

EXPO: can solve crystal structures by powder diffraction data by using reciprocal as well as

direct space methods. It is able to carry out the full pathway of the solution process: indexing,

space group determination, estimation of the integrated intensities, ab-initio and non ab-initio

structure solution, Rietveld refinement. With respect to the previous version, EXPO2014 has

been enriched with new powerful computing tools for enhancing the structure solution

process.
FOX: program was made for the ab initio crystal structure solution from diffraction data

(mostly powder diffraction data). Its most interesting features for ab initio structure

determination are:

 a versatile description of the crystal contents.

 an automatic correction for special positions and shared atoms between polyhedra,

suitable for global optimization algorithms.

 the ability to use simultaneously multiple powder patterns (X-rays, neutrons), as well as

single crystal data (e.g. extracted from a powder pattern)

 smart global optimization algorithms which can get out of false minima.

 a graphical interface (see the screenshots) with a 3D crystal structure view, with live

updates during the optimization process.

[12] What is the Xr-ay absorption?

X-ray absorption spectroscopy (XAS) is a widely used technique for determining the local

geometric and/or electronic structure of matter. The experiment is usually performed at

synchrotron radiation facilities, which provide intense and tunable X-ray beams. Samples can

be in the gas-phase, solution, or as solids. XAS data is obtained by tuning the photon energy,

using a crystalline monochromator, to a range where core electrons can be excited.

[13] What is the difference between X-ray absorption and X-ray diffraction for application?

X-ray diffraction is a technique in which diffraction of X rays with the crystal lattice are

observed. X rays which are diffracted at Bragg's angle are diffracted and combine to give a

pattern which shows about the planes in the crystal. X ray diffractogram is resulted and the

position and intensity of the peaks are observed. In short, XRD is used to determine crystal

structure and degree of crystallinity of a material. Probes average, long range structure (>10

nm). Probes crystalline phase only.

While X-ray absorption is a technique where the absorption of X-rays in the material and then
emission of other x rays which are resulted due to interaction of incident x rays with the

electrons are observed. The emitted rays have a specific energy depending on the elements

present in the material and are analyzed by spectrometer. By this method elemental

composition of the material is determined. Probes local structural environment (<1 nm).

Probes local environment of element irrespective of crystalline particle size, of

crystalline/amorphous solid, solution, gases, etc.

[14] Compare or explain the X-ray absorption process using photoelectric effect.

In this process, an x-ray photon is absorbed by an electron in a tightly bound quantum core

level (such as the 1s or 2p level) of an atom. In order for a particular electronic core level to

participate in the absorption, the binding energy of this core level must be less than the

energy of the incident x-ray. In this case, the x-ray is destroyed (i.e., absorbed) and any energy

in excess of the electronic binding energy is given to a photo-electron that is ejected from

the atom.

Following an absorption event, the atom is said to be in an excited state, with one of the core

electron levels left empty (a so-called core hole), and a photo-electron. The excited state will

eventually decay typically within a few femtoseconds of the absorption event.

There are two main mechanisms for the decay of the excited atomic state following an x-ray
absorption event. The first of these is x-ray fluorescence, in which a higher energy electron

core-level electron fills the deeper core hole, ejecting an x-ray of well-defined energy. The

second process for de-excitation of the core hole is the Auger Effect, in which an electron

drops from a higher electron level and a second electron is emitted into the continuum (and

possibly even out of the sample).

[15] Explain the following EXAFS keyword

K: K-edge is the binding energy of the K-shell (1s) electron of an atom. In order to
photoelectric absorption of the photons occurs, the photons must have more energy than the
binding energy of the K-shell electrons (K-edge).

LI, LII, LIII: LI edge corresponds to the excitation of a 2s electron which requires more energy
than a 2p electron. The 2p electron excitation is split into two edges namely LII and LIII, as a
2p electron gets excited, an open shell 2p5 electronic configuration forms, consequently, spin–
orbit coupling of such a system occurs. A 2p5 excited states corresponds to two terms,
2P1/2 which has higher energy and give rise to the LII edge, and 2P3/2 which has lower energy
and give rise to the LIII edge. Due to degeneracy, the LIII edge has twice the edge jump of the
LII and LI edges.

Destructive interference: the interference of two waves of equal frequency and opposite
phase, resulting in their cancellation where the negative displacement of one always coincides
with the positive displacement of the other.

Constructive interference: the interference of two or more waves of equal frequency and
phase, resulting in their mutual reinforcement and producing a single amplitude equal to the
sum of the amplitudes of the individual waves.

Multiple scattering: Scattering is a general physical process where radiation is forced to

deviate from a straight trajectory by one or more paths due to localized non-uniformities in

the medium through which they pass. The types of non-uniformities which can cause

scattering are known as scatterers or scattering centers It is very common that scattering

centers are grouped together; in such cases, radiation may scatter many times, in what is
known as multiple scattering.

[16] What is the benefit of Laboratory EXAFS compared to Synchrotron Radiation EXAFS?

Reliable structural information with the EXAFS technique can only be obtained from high

quality experimental data. In order to get a sufficient signal to noise ratio high intensity

radiation is required. Synchrotron radiation is extremely suitable for EXAFS experiments.

Disadvantages of the use of synchrotron radiation are: limited availability of beamtime, high

cost and sometimes unreliable operation. Laboratory EXAFS spectrometer has been developed

for rapid and ease collection of high-quality EXAFS data. It enables unlimited use of instrument,

special samples, in-situ etc.

[17] What is Boltzmann statistics in NMR?

When a group of spins is placed in a magnetic field, each spin aligns in one of the two
possible orientations. At room temperature, the number of spins in the lower energy level,
N+, slightly out numbers the number in the upper level, N-. Boltzmann statistics tells us that
𝑁 − ⁄𝑁 + = 𝑒𝑥𝑝(−𝐸⁄𝑘𝑇) where E is the energy difference between the spin states; k is
Boltzmann's constant, 1.3805 x 10-23 J/Kelvin; and T is the temperature in Kelvin. As the
temperature decreases, so does the ratio N- /N+. As the temperature increases, the ratio
approaches one.
The signal in NMR spectroscopy results from the difference between the energy absorbed by

the spins which make a transition from the lower energy state to the higher energy state, and

the energy emitted by the spins which simultaneously make a transition from the higher

energy state to the lower energy state. The signal is thus proportional to the population

difference between the states.

[18] Define SpinPacket in NMR

A spin packet is a group of spins experiencing the same magnetic field strength. In this

example, the spins within each grid section represent a spin packet.
At any instant in time, the magnetic field due to the spins in each spin packet can be

represented by a magnetization vector. The size of each vector is proportional to (N+ - N-).

The vector sum of the magnetization vectors from all of the spin packets is the net

magnetization.

[19] Explain NMR experiment using Continuous Wave mode.

The simplest NMR experiment is the continuous wave (CW) experiment. There are two ways

of performing this experiment. In the first, a constant frequency, which is continuously on,

probes the energy levels while the magnetic field is varied. The energy of this frequency is

represented by the blue line in the energy level diagram. The CW experiment can also be

performed with a constant magnetic field and a frequency which is varied. The magnitude of

the constant magnetic field is represented by the position of the vertical blue line in the

energy level diagram.

[20] Why FT NMR is more popular than CW NMR?

 If a signal is weak, many scans must be averaged to enhance the signal/noise ratio.

Signal/noise ratio rises as the square root square root of number of scans. Only FT

instruments can obtain a large number of scans in a reasonable time.

 A scan can be performed much more quickly. CW-NMR: 5 minutes; FT-NMR: 5 seconds.

[21] Define the following NMR keyword and explain it

Spin: Spin is a fundamental property of nature like electrical charge or mass. Spin comes in

multiples of 1/2 and can be + or -. Protons, electrons, and neutrons possess spin. Individual

unpaired electrons, protons, and neutrons each possesses a spin of 1/2. In the deuterium

atom (2H), with one unpaired electron, one unpaired proton, and one unpaired neutron, the

total electronic spin = 1/2 and the total nuclear spin = 1.

gyromagnetic ratio: In physics, the gyromagnetic ratio of a particle or system is the ratio of

its magnetic moment to its angular momentum, and it is often denoted by the symbol . Its

SI unit is the radian per second per tesla (rad⋅s− 1⋅T− 1) or, equivalently, the coulomb per

kilogram (C⋅kg− 1). When placed in a magnetic field of strength B, a particle with a net spin

can absorb a photon of frequency . The frequency depends on the gyromagnetic ratio,  of
the particle.  = 𝛾 ∙ 𝐵. For hydrogen,  = 42.58 MHz / T.

Energy level: When collection of identical nuclei is placed in a strong external magnetic field

B, an interaction will occur between each individual nuclear magnetic vector and this field.

Therefore, two groups of nuclei appear according to the direction of their spin vector, whose

energies correspond to low energy state E1 and to high energy state E2. These orientations

are called ‘spin up’ (magnet image N-S-N-S) and ‘spin down’ (N-N-S-S).

Transition: A particle can undergo a transition between the two energy states by the

absorption of a photon. A particle in the lower energy state absorbs a photon and ends up

in the upper energy state. The energy of this photon must exactly match the energy difference

between the two states. The energy, E, of a photon is related to its frequency,  (Larmor

frequency), by Planck's constant (h = 6.626 x 10-34 J s). 𝐸 = ℎ ∙ .

Rotating frame: A rotating frame of reference rotates about the Z axis at the Larmor frequency.

This rotating coordinate system can be distinguished from the laboratory system by primes

on the X and Y axes, X'Y'. A magnetization vector rotating at the Larmor frequency in the

laboratory frame appears stationary in a frame of reference rotating about the Z axis.

Pulsed magnetic field: A coil of wire placed around the X axis will provide a magnetic field

along the X axis when a direct current is passed through the coil. An alternating current will

produce a magnetic field which alternates in direction. In magnetic resonance, the magnetic

field created by the coil passing an alternating current at the Larmor frequency is called the

B1 magnetic field. When the alternating current through the coil is turned on and off, it creates

a pulsed B1 magnetic field along the X' axis. The spins respond to this pulse in such a way as

to cause the net magnetization vector to rotate about the direction of the applied B1 field.
Spin relaxation: In NMR spectroscopy spin relaxation describes how net magnetization vector

returns to its equilibrium value after the nuclear spin system is exposed to energy of a

frequency equal to the difference between the spin states. Motions in solution which result in

time varying magnetic fields cause spin relaxation. Time varying fields at the Larmor frequency

cause transitions between the spin states and hence a change in MZ.

Free induction decay: In FT NMR, free induction decay (FID) is the observable NMR signal

generated by non-equilibrium nuclear spin magnetization precessing about the magnetic field

(conventionally along z). This non-equilibrium magnetization can be induced, generally by

applying a pulse of resonant radio-frequency close to the Larmor frequency of the nuclear

spins.

[22] What is the difference between T1 and T2?

It is possible to change the net magnetization by exposing the nuclear spin system to energy

of a frequency equal to the energy difference between the spin states. If enough energy is
put into the system, it is possible to saturate the spin system and make MZ=0.

The time constant which describes how MZ returns to its equilibrium value is called the spin

lattice relaxation time (T1). The equation governing this behavior as a function of the time t

after its displacement is: 𝑀𝑧 = 𝑀𝑜 (1 − 𝑒 −𝑡⁄𝑇1 )

If the net magnetization is placed in the XY plane it will rotate about the Z axis at Larmor

frequency. The time constant which describes the return to equilibrium of the transverse

magnetization, MXY, is called the spin-spin relaxation time, T2. 𝑀𝑋𝑌 = 𝑀𝑋𝑌𝑜 𝑒 −𝑡⁄𝑇2

[23] Define the Deshielding effect and the chemical shift and explain it.

In some cases, such as the benzene molecule, the circulation of the electrons in the aromatic

 orbitals create a magnetic field at the hydrogen nuclei which enhances the Bo field. This
phenomenon is called deshielding. In this example, the Bo field is applied perpendicular to

the plane of the molecule. The ring current is traveling clockwise if you look down at the

plane.

The electron density around each nucleus in a molecule varies according to the types of nuclei

and bonds in the molecule. The opposing field and therefore the effective field at each nucleus

will vary. This is called the chemical shift phenomenon.

The chemical shift of a nucleus is the difference between the resonance frequency of the

nucleus and a standard, relative to the standard. This quantity is reported in ppm and given

the symbol delta, . 𝛿 = ( − 𝑅𝐸𝐹 ) × 106 /𝑅𝐸𝐹 .

[24] What is the Spin-Spin coupling?

Nuclei experiencing the same chemical environment or chemical shift are called equivalent.

Those nuclei experiencing different environment or having different chemical shifts are

nonequivalent. Nuclei which are close to one another exert an influence on each other's

effective magnetic field. This effect shows up in the NMR spectrum when the nuclei are

nonequivalent. If the distance between non-equivalent nuclei is less than or equal to three

bond lengths, this effect is observable. This effect is called spin-spin coupling or J coupling.

Consider the following example. There are two nuclei, A and B, three bonds away from one

another in a molecule. The magnetic field at nucleus A will be either greater than Bo or less

than Bo by a constant amount due to the influence of nucleus B.

[25] what is the role of Fourier transform in Time domain NMR?

A Fourier transform is an operation which converts functions from time to frequency domains.

An inverse Fourier transform (IFT) converts from the frequency domain to the time domain.

A magnetization vector, starting at +x, is rotating about the Z axis in a clockwise direction.

The plot of Mx as a function of time is a cosine wave. Fourier transforming this gives peaks at

both + and - because the FT cannot distinguish between a + and a - rotation of the

vector from the data supplied.

A plot of My as a function of time is a -sine function. Fourier transforming this gives peaks at

+ and - because the FT cannot distinguish between a positive vector rotating at at + and

- a negative vector rotating at - from the data supplied.

The solution is to input both the Mx and My into the FT. The FT is designed to handle two

orthogonal input functions called the real and imaginary components. Detecting just the Mx
or My component for input into the FT is called linear detection. Detection of both Mx and

My is called quadrature detection.

[26] What is the effect on NMR experiment when the molecular motion is restricted?

Spatial proximity and/or a chemical bond between two atoms can give rise to interactions

between nuclei. In media with no or little mobility (e.g. crystals, powders, large membrane

vesicles, molecular aggregates), anisotropic interactions have a substantial influence on the

behavior of a system of nuclear spins. Two directionally dependent interactions commonly

found in solid-state NMR are the chemical shift anisotropy (CSA) and the internuclear dipolar

coupling. Many more such interactions exist, such as the anisotropic J-coupling in NMR.

Anisotropic interactions between nuclei, which are usually averaged by Brownian motion in

liquid samples, cause significant line broadening in solid state NMR.

[27] How can you remove the effect on the NMR experiment when the molecular motion

is restricted, especially in solid state?

Several methods have been developed and considered in order to minimize large anisotropic

NMR interactions between nuclei and increase signal in rare spin NMR spectra:

 Magic-angle spinning: By spinning the sample (usually at a frequency of 1 to 130 kHz,

depending on the rotor size and type of experiment being conducted) at the magic angle
 θm (ca. 54.74°, where cos2θm=1/3) with respect to the direction of the magnetic field, the

normally broad lines become narrower, increasing the resolution for better identification

and analysis of the spectrum.

 Advanced Pulse Techniques: Pulse sequences are used to excite signals and to looks for

“free induction decay” and “spin echoes” that are observed in an NMR spectrometer. They

range from general purpose single-pulse experiments to complex highly sophisticated

experiments that select specifically interacting nuclei.

[28] What is the CP-MAS?

In cross-polarization/magic angle spinning technique, polarization from abundant spins is

transferred to dilute spins. The overall effect is to enhance signal:

 Cross polarization enhances signal from dilute spins potentially by a factor of 𝐼 ⁄𝑆 ,

where I is the abundant spin and S is the dilute spin.

 Since abundant spins are strongly dipolar coupled, they are therefore subject to large

fluctuating magnetic fields resulting from motion. This induces rapid spin-lattice

relaxation at the abundant nuclei. The end result is that one does not have to wait for

slowly relaxing dilute nuclei to relax.

Polarization is transferred during the spin locking period, (the contact time) and a /2 pulse

is only made on protons:

The key to obtaining efficient cross polarization is setting the Hartmann-Hahn match properly.

[29] What happen when the solid sample rotates in MAS NMR?

By spinning the sample (usually at a frequency of 1 to 130 kHz, depending on the rotor size

and type of experiment being conducted) at the magic angle θm (ca. 54.74°, where cos2θm=1/3)
with respect to the direction of the magnetic field, the normally broad lines become narrower,

increasing the resolution for better identification and analysis of the spectrum. The rate of

MAS must be greater than or equal to the magnitude of the anisotropic interaction to average

it to zero.

[30] What is the Spinning rate and resulting effect on the NMR spectrum?

By spinning the sample (usually at a frequency of 1 to 130 kHz, depending on the rotor size

and type of experiment being conducted) at the magic angle θm (ca. 54.74°, where cos2θm=1/3)

with respect to the direction of the magnetic field, the normally broad lines become narrower,

increasing the resolution for better identification and analysis of the spectrum. The rate of

MAS must be greater than or equal to the magnitude of the anisotropic interaction to average

it to zero.
[31] Please explain the real image and reciprocal space image in EM using Fourier

transform.

A real space shift results in multiplication with a phase factor in reciprocal space:

Mathematically, the objective lens performs

1) A Fourier transform FT (Fourier analysis) that creates the diffraction pattern of the object

in the back focal plane. The diffraction pattern is the Fourier transform of the scattered

electron wave: in turn the primary image is the Fourier transform of the diffraction pattern,

and

2) An inverse FT (Fourier synthesis) that makes the interference of the diffracted beams back

to a real space image in the image plane (lattice image).

The Fourier transform decomposes a function into a continuous spectrum of its frequency

components. The Fourier transform of 𝑓(𝑥) is defined as:

The diffraction pattern from a thin specimen can be considered as the Fourier transform (FT)

of the specimen.

The “reciprocal lattice vectors” a∗, b∗ and c∗ generate the “reciprocal lattice”:
[32] What is the difference between ED and XRD?

Both, ED and XRD, are caused by constructive interference of scattered waves, and the same

fundamental laws (e.g., Bragg law, extinction rules) can be applied for the interpretation of

the resulting diffraction patterns. In both cases, diffraction patterns of powders and of single

crystals appear.

However, ED and XRD show some distinct differences:

1. The wavelength of electrons (e.g., 1.97 pm for 300 keV electrons) is much shorter than

that of X-rays (about 100 pm). Therefore, the radius of the Ewald sphere is much larger

and more reflections are observed by ED than by XRD.

2. The diffraction angles are very small in ED: 0 < Θ < 2° (cf., XRD: 0 < Θ < 180º)
3. Electrons are scattered by the positive potential inside the electron cloud (Coulomb

interaction), while X-rays interact with the electron cloud. As the result, the interaction of

electrons with matter is much stronger (106-107×) than that of X-rays.

This has the advantage that the diffracted electron beams have a high intensity and exposure

times are in the order of a few seconds. ED patterns can directly be observed on the viewing

screen of the electron microscope. Thus, orienting a crystal along a direction can be easily

achieved by tilting while observing changes of the ED pattern simultaneously. Furthermore,

diffraction patterns can be obtained from very small crystals selected with a diffracted aperture

(Selected Area Electron Diffraction SAED) and by a focused electron beam even from nm-

sized regions (Convergent Beam Electron Diffraction CBED).

The disadvantage of the strong interaction is that multiple scattering plays an important role,

and the intensities of the reflections are much influenced by this dynamical effect. This makes

structure determination from ED more difficult and less reliable than that from XRD data. A

method for getting more reliable quantitative data is precession diffraction.

[33] Is possible to use ED for the structural determination of powder sample and justify

your answer.

Electron crystallography (EC) is another most valuable technique for structure determination.

With the electron as a probe, EC alone can also be used for structure determination, especially

for crystals that are too small to be studied by SCXRD or too complex for PXRD. As electrons

interact much more strongly with matter than X-rays do, both electron diffraction (ED) patterns

and high-resolution transmission electron microscopy (HRTEM) images can be obtained from

nanosized crystals. Nano- and micrometer-sized crystals can be treated as single crystals in

EC, whereas they are considered to be powders in X-ray diffraction. The reflections in ED

patterns are completely separated, and the structure factors, including amplitudes and phases,

can be obtained directly from high-resolution transmission electron microscopy (HRTEM)

images, making EC a powerful method to determine structures, especially for impure samples.

However, collecting a complete set of ED patterns or recording a good HRTEM image requires

considerable expertise on the operation of electron microscopes and crystallography. The

strong interactions between electrons and materials can also lead to dynamical effects and

beam damage. These difficulties make structure determination from ED patterns and HRTEM

images not straightforward. All in all, EC and X-ray crystallography are remarkably

complementary.

[34] When you combine the EM and EDX, what kind of information is available?

Energy Dispersive X-Ray Spectroscopy (EDS or EDX) is a chemical microanalysis technique

used in conjunction with scanning electron microscopy (SEM). he EDS technique detects x-

rays emitted from the sample during bombardment by an electron beam to characterize the

elemental composition of the analyzed volume. Features or phases as small as 1 µm or less

can be analyzed.

When the sample is bombarded by the SEM's electron beam, electrons are ejected from the

atoms comprising the sample's surface. The resulting electron vacancies are filled by electrons

from a higher state, and an x-ray is emitted to balance the energy difference between the

two electrons' states. The x-ray energy is characteristic of the element from which it was

emitted. The EDS x-ray detector measures the relative abundance of emitted x-rays versus

their energy. The spectrum of x-ray energy versus counts is evaluated to determine the

elemental composition of the sampled volume.