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Physical Methods in Inorganic Chemistry .
Presentation · February 2014

DOI: 10.13140/RG.2.2.14093.23527/1
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Physical Methods in Inorganic
Chemistry
Dr. Mutasem Z. Bani Fwaz
1
Electronic Structure and Spectroscopy of TM
Complexes:
UV-Visible Spectroscopy
Magnetic Susceptibility
Dr.Mutasem Z. Bani Fwaz

Chem 522
Electronic Spectroscopy
 Spectroscopy involving energy level transitions of the
electrons surrounding an atom or a molecule
Atoms: electrons are in Molecules: electrons are in
hydrogen-like orbitals molecular orbitals (HOMO,
(s, p, d, f) LUMO, …)
From
http://education.jlab.org
(The Bohr model for nitrogen) (The LUMO of benzene)

UV-Visible Spectroscopy
 Definition: Spectroscopy in the optical (UV-Visible) range
involving electronic energy levels excited by
electromagnetic radiation (often valence electrons).
Dr. Mutasem Zaki Bani Fawaz 6
How do we label states?
Each electronic state has its own term symbol
Use Russell Saunders Coupling to describe electron-electron repulsion
orbital angular momentum
L=0 S term
When considering
spin multiplicity 2S+1 L=1 P term
LJ L=2
L=3
D term
F term
symmetry use the
Mulliken symbol
spin orbit coupling

J = |L+S| ...|L-S|
L = 0, 1, 2…total orbital angular momentum (term)
ML = -L…+L component of L (ML = S ml)
S = total spin quantum number (S = S s)
Ms = -S….+S component of S (MS = S ms)
Within each term, there can be several degenerate microstates with different ML and MS
Question-1-: What is the ground state term symbol for the
following atoms 3Li, 14Si and 21Sc?
Note: ground state term symbol for lowest energy configuration.
You must know the following rearrangement to do that and

answer the question above:
s-orbital
ml 0
p-orbitals
ml +1 0 -1
d-orbitals
ml +2 +1 0 -1 -2
f-orbitals
ml +3 +2 +1 0 -1 -2 -3 8
Dr. Mutasem Zaki Bani Fawaz
3Li: 1s22s1
2S + 1 = 2(1/2) + 1 = 2
J = L + S.... ...
symbol L = 0 S
ml 0 untile absolute value of
term symbol 2S
1/2
S ml = 0 L -S
S ms = + 1/2
J = 1/2
2S
1/2
most stable
21Sc: 1s22s22p63s23p63d14s2
2S + 1 = 2(1/2) + 1 = 2
ml +2 +1 0 -1 -2
L=2 D 2D
S ml = 2 5/2
S ms = +1/2 J = 5/2 and 3/2 2D

3/2 most stable
S ml = +1 + 0 = 1
2S + 1 = 2(1) + 1 = 3
S ms = +1/2 +1/2 = +1
L=1 P
14Si: 1s22s22p63s23p2 J = 2, 1, 0
3P , 3P , 3P
2 1 0
3P
ml +1 0 -1 0 most stable
9
Why Molecular term symbols are important?
As soon as ligands are coordinated to a transition-metal centre, a molecular symmetry
is imposed and the d orbital split according to the ligand field. In these cases,
molecular term symbols have to be used.
Term Components in an octahedral field
S A1g
P T1g
D T2g+ Eg
F A2g + T2g + T1g
G A1g + Eg + T2g + T1g
H Eg + 2 T1g + T2g
I A1g + A2g + Eg + T1g + 2 T2g
Similar splittings occur in a tetrahedral field, but the g labels are no longer applicable.

Selection rules
(determine intensities)
Laporte rule
g  g forbidden (that is, d-d forbidden)
but g  u allowed (that is, d-p allowed)
Spin rule
Transitions between states of different multiplicities forbidden
Transitions between states of same multiplicities allowed
These rules are relaxed by molecular vibrations, and spin-orbit coupling
11
Spectrochemical series

‫السؤال الذي يطرح نفسه كيف نستفيد من الحدود الطيفية بتفسير االطياف واالشارات في اطياف‬
‫االشعة المرئية والفوق بنفسجية لمحاليل المركبات التناسقية للعناصر االنتقالية‬
‫لذلك سوف نستعرض السؤال والحل له التالي للتفسير‬
‫‪Question and answer‬‬ ‫‪Question-2-:‬‬

‫‪Explain the spectrum below for‬‬ ‫‪3d3‬‬ ‫‪in octahedral week ligand‬‬
‫?‪environment‬‬
‫‪Dr. Mutasem Zaki Bani Fawaz‬‬ ‫‪13‬‬

Qualitative Explanation
Consider a d3 system complex in
octahedral environment.
The ground state configuration is:
________ A transition from the
dz2 dx2-y2 dxy to the dx2-y2, or the
dyz or dxz to the dz2
____ ____ ____ orbitals involve a
relatively
dxy dyz dxz minor change in
environment.
Qualitative Explanation
Since the promotion of an electron from
the t2g set of orbitals to the eg set can
involve differing changes in environment,
several peaks will be seen in the
spectrum.
d-orbitals
ml +2 +1 0 -1 -2
ML = 2 +1 +0 = 3
or L = 3
MS = 1/2 + 1/2 + 1/2 = 3/2 = S

or S = 1
2S + 1 = 2 x 3/2 + 1 = 4
4F

Magnetic Susceptibility
• Magnetic Properties reveal numbers of unpaired electrons
• Hund’s Rule requires maximum number of unpaired electrons in
degenerate orbitals
not
• Magnetic Descriptions
– Diamagnetic = all paired electrons = slightly repelled by magnetic
field
– Paramagnetic = unpaired electrons = strongly attracted by magnetic
field
• Magnetic properties are determined by one of several experimental
methods

Molar Magnetic Susceptibility = cM = cm3/mol = data from an experimental
determination
Magnetic Moment = Calculated value from cM and theoretical treatment of
magnetism. m = Bohr magnetons
Theoretical basis of magnetism
– Electron Spin: a spinning charged particle would generate a spin
magnetic moment = mS (not really spinning but a property of an
electron)
– mS = + ½ or – ½ only because the electron can either “spin” clockwise

or counter clockwise (up or down arrows)
– S = Spin Quantum Number = S mS

» Example: S = 3(+ ½ ) = 3/2
» Example: S = +1/2 ms  2 S ( S  1)
ms  n(n  2)
Question and answer Question-3-: : calculate mS for high spin Fe3+
» Determine d-electron count by using the periodic table
For iron (3+) and counting the capacity of d-orbitals by
electrons : 3d5
» Arrange the d-electrons in the 5d-orbitals as high spin
» Apply mS = g[S(S+1)]½ = 2[5/2(7/2)]½ = 5.92 Bohr

magnetons
Or [n(n+2)] ½ = [5(7)] ½ = (35) ½ = 5.92

Magnetic properties
The spin-only formula applies reasonably well to metal ions from the
first row of transition metals: (units = μB,, Bohr-magnetons)
Metal ion dn configuration μeff(spin only) μeff (experimently)

Ca2+, Sc3+ d0 0 0
Ti3+ d1 1.73 1.7-1.8
V3+ d2 2.83 2.8-3.1
V2+, Cr3+ d3 3.87 3.7-3.9
Cr2+, Mn3+ d4 4.90 4.8-4.9
Mn2+, Fe3+ d5 5.92 5.7-6.0
Fe2+, Co3+ d6 4.90 5.0-5.6
Co2+ d7 3.87 4.3-5.2
Ni2+ d8 2.83 2.9-3.9
Cu2+ d9 1.73 1.9-2.1
Zn2+, Ga3+ d10 0 0
Homework-1-.
Q1) The [Ni(pyridine)4(H2O)2]Br2 has d-d absorption

bands at 27,000, 16,500, and 10,150 cm-1. No symmetry
splitting is observed, explain your answer?
Q2) Calculate the spin-only magnetic moment for

[Ni(H2O)6]Cl2.

Q3) Indicate the oxidation number of the
central atom and the term symbol for the
ground state in each of the following
complexes.
a) [Pt(CN)4]2-
b) [Cr(NH3)6](NO3)3
c) Na2[CdCl4]
d) [Co(H2O)5Cl]2+
e) K3[V(C2O4)3]

IR-Spectroscopy
Dr.Mutasem Z. Bani Fwaz

Dr. Mutasem Z. Bani Fwaz 2
Dr. Mutasem Z. Bani Fwaz 3
HOMO:s
LUMO:p*
4
Some interested Ligands
h
x
M
M
M
M
M
h5-Cp h3-Cp h3-allyl h1-allyl

6e-(-1) 4e-(-1) 4e-(-1) 2e-(-1)
mx - bridging ligand

4e(-1)
2e(-1)

4e(-1)
- -
-
2e(-1)
6e(-1)

Ligands
Common Organic Ligands
2e(0)
h6- 6e(0)
4e (-2)
6e(-3) 4e(0)
- h3- 4e(-1) 2e(0)
2e(0) or 4e(0)
4e(-1)
-2 h4- 6e(-2)
2e(-1)
- h5- 2e(-1)
6e(-1)
B) Binding Modes Ligands and Nomenclature CO, N2, PR3, H2, NH3
All neutral 2e(0)
1) Bridging is possible with organometallic ligands
h1-C6H5 2e(-1)
CN-, Cl-, Br-, I-, H-

2e(-1)
8
Examples of Electron Counting
1) Cr(CO)6
– Total charge on ligands = 0, so charge on Cr = 0, so Cr = d6
– 6 CO ligands x 2 electrons each = 12 electrons
– Total of 18 electrons
2) (h5-C5H5)Fe(CO)2Cl
– Total charge on ligands = 2-, so Fe2+ = d6
– (h5-C5H5- = 6) + (2CO x 2 = 4) + (Cl- = 2) = 12 electrons
– Total of 18 electrons
3) Charged complex: [Mn(CO)6]+

– Total ligand charge = 0, so Mn+ = d6
– 12 electrons from 6 CO ligands gives a total of 18 electrons
4) M—M Bond: (CO)5Mn—Mn(CO)5

– Each bond between metals counts 1 electron per metal: Mn—Mn = 1 e-
– Total ligand charge = 0, so Mn0 = d7
– 5 CO ligands per metal = 10 electrons for a total of 18 electrons per Mn

Why we need MO diagram for
diatomic molecules
As bond order increase the bond energy increase and bond distance or
length decrease and IR frequency increase
HOMO:highest occupied molecular orbital

LUMO:lowest unoccupied molecular orbital

18
Infrared Spectroscopy
1) Number of Bands is determined by group theory
2) Position of IR Bands
a) Electron Density determines Wavenumbers
Cr(CO)6 n = 2000 cm-1 [V(CO)6]- n = 1858 cm-1 [Mn(CO)6]+ n = 2095 cm-1
Phosphine's

Homework-2-.
Q1) For each of the following pairs of metal complexes,
circle the one that should have the highest average carbonyl
IR stretching frequency. What does this tell you about the
relative electron density on the metal centre (electron-rich or deficient)?
Briefly discuss your reasoning for each case.
a) [Rh(CO)4]1- or [Fe(CO)4]2-
b) (PF ) Mo(CO) or (PCl3)3Mo(CO)3
3 3 3

Q2) The IR spectrum below shows signals due to CO stretching frequency, draw
out suitable structure which fit the molecular formula Fe2(CO)9, Briefly discuss
your answer?

Q3) Explain the differences in the IR CO stretching frequencies of
the following two complexes. Fe(CO)5 2025 and 2000 cm-1 and
Fe(CO)3(PPh3)2 1944, 1886 and 1881 cm-1.

Q4) (h5-Cp)2Co2(CO)3 has IR bands at 1965 cm-1 and 1812 cm-1 but (h5-
Cp)2Co2(CO)2 has only a single band at 1792 cm-1. Provide structures for both
molecules that are consistent with the data and the 18 e- rule. Show clearly the
number of M-M bonds in each structure.

Q5) Consider the compound (h5-Cp)2Co2(CO)2 has IR band at 2000 cm-1.
Provide structure for molecule that is consistent with the data and the 18 e- rule.
Show clearly the number of M-M bonds.

MS
Mass Spectrometry
Isotope
patterns
63Cu35Cl
63Cu: 69.1% 35Cl: 63Cu37Cl
75.5%
65Cu: 30.9% 37Cl: 24.5% 65Cu35Cl
65Cu37Cl
Abundance of first isotope peak M: .691 x .755 = .521

For next isotope peak: M+2: .691 x .245 = .169
.309 x .755 = .233 } .403
For next isotope peak: M+4: .309 x .245 = .076
Fragmentation
1. The charge is likely to remain on Metal-containing fragment
M Ln-1+ + L
MLn
L+ + M Ln-1 Less likely
2. Rearrangement involving hydrogen migration are frequent

R (M => Si, Ge, Sn, Pb…)
R R
M H2C CH2
M H
H R
R
R M O R
M H
MeHC O
H R
CH3
Rearrangement process
“McLafferty” type of rearrangement involving metal instead of H
+ +
MR3 MR3
H2C O CH2 O
+
H2C CH2
CH2 R R
H2C
This rearrangement depends on readiness of metal to

become pentacoordinate (using it’s d-orbitals)
Observed in: Keto-organotin: RCO (CH2)3 Sn (CH3)3

Influence of operating conditions
Electron deficient Alkyls and Aryls groups gives information about
molecular complexity of the vapor.
Ethyl Lithium: produce following ions:
Li6Et5+
Li5Et4+
Li4Et3+ All these can be derive from the
Li3Et2+ hexamer Li6Et6
Li2Et+
Li+
In Electron deficient compounds of group II and III (Be and Al),

monomeric molecules are associated by weak bridging bonds
Metal Carbonyls (Co)
Metal Carbonyls (Fe)
Metal Carbonyls (Fe)
Review
Q1: What are mass percents of Na, H, C, and O in NaHCO3?
Soln: Molecular mass of NaHCO3 =
(1 x Na) + (1 x H) + (1 x C) + (3 x O)
(1 x 23) + (1 x 1) + (1 x 12) + (3 x 16) = 84 g/mol
% of Na = 1 x 23 X 100 = 27.38 %
84
1x1
% of H = X 100 = 1.19 %
84
1 x 12
% of C = X 100 = 14.28 %
84
% of O = 3 x 16
X 100 = 57.14 %
84
9
Q2:
Fe2O3. 3/2 H2O
The molecular mass of limonite

= (2 x Fe) + (3 x O) + 3/2 (H2O)
= (2 x 56) + (3 x 16) + 3/2 (18) = 186.7
g/mole
Simplest Formula [Empirical Formula] from Chemical analysis
Q3: A 25.0 g sample of an orange compound contains 6.64 g of

potassium (K), 8.84 g of chromium (Cr) and 9.52 g of oxygen (O).
Find the empirical formula. [Ar of K = 39.19 & Cr = 52 & O = 16]
Answer: no of moles of (K) = 6.64 / 39.19 = 0.17 mole
no. of moles of (Cr) = 8.84 / 52 = 0.17 mole
no. of moles of (O) = 9.52 / 16 = 0.595 mole
To know the empirical formula divided by the smallest no. of moles
i.e. 0.170
No. of (K) atoms in the simplest formula = 0.170 / 0.170 = 1 (K)
No. of (Cr) atoms in the simplest formula = 0.170 / 0.170 = 1 (Cr)
No. of (O) atoms in the simplest formula = 0.595 / 0.170 = 3.5 (O)
The simplest formula KCrO3.5
The empirical formula is K2Cr2O7
Q4) Nicotine is a natural product found in tobacco leaves. It can act as a stimulant or a
depressant. It is 74.03% C, 8.70% H, and 17.27% N. Its molecular weight is 162.24 g/mol.
a. What is the empirical formula of nicotine?
b. What is the molecular formula of nicotine?

NMR
Nuclear Magnetic Resonance
NMR for Organometallic compounds
Electron Paramagnetic Resonance

Electron Spin Resonance
Basic principles of
Mössbauer spectroscopy
Summary 2nI+1
The number of components into which a signal is split is 2nI+1, where I is the spin quantum number and
n is the number of other nuclei interacting with the nucleus.
For proton, I = 1/2
Neighbor group has one proton
Neighbor group has two protons
Neighbor group has three protons
Two neighbor groups have one proton each

classification of the nuclei
• I = 1/2, 100%abundance 1H, 31P, 19F, 103Rh
• I = 1/2, low abundance 13C, 15N, 29Si, 77Se,
109Ag, 119Sn, 125Te,
183W, 195Pt, 199Hg
• I > 1/2, 100% abundance 14N, 27Al, 51V, 59Co
• I > 1/2, low abundance 11B, 121Sb, 193Ir

relative NMR
frequency (MHz) standard compound common
nucleus (B0 = 4.7 T) reference range (ppm) 1
1H 200.0 (CH3)4Si -30 – 20
13C 50.2 (CH3)4Si -100 – 400
19F 188.2 CFCl3 -200 – 200
29Si 39.8 (CH3)4Si -350 – 40
31P 81.0 85% aq. H 3PO4 -100 – 250
77Se 38.2 (CH3)2Se -300 – 200
119Sn 74.5 (CH3)4Sn -1000 – 8000
195Pt 43.0 [Pt(CN)6]2- -200 – 15000
4e(-1)
2e(-1)

Pi bonds do not count toward this bond limit, but J may be too small to observe
free spacer
Hb Hc •Ha couples with Hb
C C •Ha couples with Hc
Ha C •Ha couples with Hd but J may be very small
Hd

11
Alkali organometallics: Organolithium
For Lithium: we have the choice between 2 nuclei:
6Li : Q=8.0*10-4 a=7.4% I=1
7Li : Q=4.5*10-2 a=92.6% I=3/2
6Li : Higher resolution 7Li : Higher sensitivity
Boron NMR
For Boron: we have the choice between 2 nuclei:
10B : Q= 8.5 * 10-2 a=19.6% I=3
11B : Q= 4.1 * 10-2 a=80.4% I=3/2
11B : Higher sensitivity
11B coupling with Fluorine: 19F-NMR
10B : Q= 8.5 * 10-2 a=19.6% n=10.7 I=3 2nI+1 = 7
11B : Q= 4.1 * 10-2 a=80.4% n=32.1 I=3/2 2nI+1 = 4
Boron can couple to other nuclei as shown here on 19F-NMR
Isotopic shift
19F-NMR
11BF
4
NaBF4 / D2O
JF-10B n10B 10BF

= 4
JF-11B n11B
JBF=0.5 Hz JBF=1.4 Hz
Coupling with Quadrupolar Nuclei (I>1/2)
Electron Paramagnetic Resonance
Electron Spin Resonance
R1 R2
OH. Mn+2 N
.
O
Free Radicals Transition Metals Spin Labels

Ascorbate All that have R1 & R2 chosen
Hydroxyl unpaired electrons to provide
Tocopherol specificity
etc.
ms = 1/2, ml = 3/2
CH3 n=3 I=1/2

[2 X 3 X (1/2)+1] = 4
CH3 the 4 lines 1:3:3:1 17

H n=1 I=1/2
[2 X 1 X (1/2)+1] = 2 lines
C H - radical anion the 7 lines

6 6
1:6:15:20:15:6:1
Examples:
AlH -
3
Al n=1 I=5/2
H n=3 I=1/2
[2 X 1 X (5/2)+1][2 X 3 X (1/2)+1]
 [6] X [4] = 24 lines

Basic principles of
Free emitting and absorbing atoms
Emission Absorption
Recoil
2 γ-ray energy
E 
Energy of recoil ER = 2
2mc Mass of atom
Appearance of Mössbauer spectra
Depending on the local environments of the Fe atoms and the magnetic
properties, Mössbauer spectra of iron oxides can consist of a singlet, a
doublet, or a sextet.
Magnetic hyperfine field

Quadrupole splitting
Isomer shift
δ Δ Bhf
Symmetric charge Asymmetric charge Symmetric or asymmetric charge
No magnetic field No magnetic field Magnetic field (internal or external)
Relative Transmission
Fe3+ Fe2+

-4 -2 0 2 4
Velocity (mm/s)
Transmission
0.41 mm/s
[ 0.00mm/s ]
-10 -5 0 5 10
Velocity (mm/s)
Strengths and weaknesses of 57Fe
Strengths Weaknesses
• Sensitive only to 57Fe • Sensitive only to 57Fe
(no matrix effects) (“sees” only 57Fe)
• Sensitive to oxidation state • Coordination ? to ±
• Allows distinction of magnetic • Paramagnetic phase data
phases often ambiguous
• Very sensitive towards • Diamagnetic element
magnetic phases substitution & relaxation
• Non-destructive • Slow
• Resolution limited by • If possible, use other
uncertainty principle techniques as well
Often a combination of Mössbauer spectroscopy with
other techniques can help solve problems that cannot
be resolved using Mössbauer spectroscopy alone.
Quiz 3
Introduction To:
Solid State Chemistry
‫الدكتور معتصم زكي بني فواز‬

‫جامعه الملك خالد‬-‫قسم الكيمياء‬
Dr.Mutasem Zaki Bani-Fawaz 1

SOLIDS
can be divided into two catagories.
 Crystalline
 Amorphous
Solids with rigid a highly regular

arrangement
Solids with considerable disorder in their

structures

Tempreture Tempreture
Time Time
Amorphous A Crystalline B
Heating curve temperature vs time A for

amorphous and B for crystalline

States of matter and enthalpy of system

Crystals are made of infinite number of unit cells
Unit Cell
Crystal lattice

 =  between b and c
  =  between c and a

  =  between a and b
A parallelepiped is generated by the vectors

a , b and c

Auguste Bravais
Lattices
(1811-1863)
• In 1848, Auguste Bravais demonstrated that

in a 3-dimensional system there are fourteen
possible lattices
• A Bravais lattice is an infinite array of
discrete points with identical environment
• seven crystal systems + four lattice centering
types = 14 Bravais lattices
• Lattices are characterized by translation
symmetry
LATTICE TYPES
Primitive ( P ) Body Centered ( I )
Face Centered ( F ) C-Centered (C )

Dr.Mutasem Zaki Bani-Fawaz Bravais lattices
10
Seven systems divide into 14 Bravais
lattices :
1. Triclinic P
2. Monoclinic P, C
3. Orthorhombic P, C, I, F
4. Trigonal P
5. Hexagonal P
6. Tetragonal P, I
7. Cubic P, I, F
The crystal lattice: one atomic basis
• The basis can also just consist of
one atom.

Point Group = Collection (group) of symmetry operators that all
pass through the same point. The group must be closed, have an
identity element, and every element must have an inverse.
Element Schoenflies Hermann- Operation
Mauguin
Rotation axis Cn n n-fold rotation (360º/n)
Identity E 1 nothing
Plane of symmetry  m Reflection
Center of symmetry i -1 or “1 bar” Inversion
Improper rotation axis Sn - n-fold rotation + reflection

Rotary Inversion axis - -n or “n bar” n-fold rotation + inversion
Space Groups = Collections of symmetry operators that are

compatible with three-dimensional crystallographic (i.e.
translational) symmetry. There are 230 space groups. Because
protein and nucleic acid molecules are chiral, there are only 65
“biological” space groups.
Symmetry Elements
Glide reflection (mirror plane + translation)
reflects the asymmetric unit

across a mirror and then
translates parallel to the mirror.
A glide plane changes the
handedness of figures in the
asymmetric unit. There are no
invariant points (points that map
onto themselves) under a glide
reflection.

Symmetry Elements
Screw axes (rotation + translation)
Screw Axis
A NM screw rotation operation consists of a 360/N rotation
followed by a displacement of M/N the unit cell dimension parallel to the axis.
For example a 31 screw axis parallel to the c-axis represents a 120 deg rotation
followed by a displacement of 1/3c.

System Required rotation symmetry
1. Cubic Three 4-fold axes, four 3-fold axes

and six 2-fold axes, 9m, i
2. Tetragonal One 4-fold axis and four 2-fold axes, 5m, i
3. Orthorhombic Three 2-fold axis, 3m, i
4. Hexagonal One 6-fold axis and six 2-fold axes, 7m, i
5.Rhombohedral One 3-fold axis and three 2-fold axes, 3m, i
6. Monoclinic One 2-fold axis, 1m, i
7. Triclinic Non axes or planes but only i

a) Monoclinic, P 21 /c b) Orthorhombic, I bca

Space group P1bar
Point group 1bar + Bravais lattice P1 bar

Lattice Sites in an Orthogonal Coordinate System
i.e. Simple Cubic

Miller Indices of directions and
planes
William Hallowes Miller

(1801 – 1880)
University of Cambridge

Miller Indices for planes
1. Select an origin not on the plane
z
(0,0,1) 2. select a crystallographic
coordinate system
3. Find intercepts along axes 2 3 1
y
(0,3,0)
4. Take reciprocal 1/2 1/3 1
5. Convert to smallest integers in the same ratio: 3 2 6

x (2,0,0)
6. Enclose in parenthesis : (326)

z
y
x

z
y
x
020 200 002

z
z
y y
x x

Early
generation
X-ray
diffractometer
Dr.Mutasem Zaki Bani-Fawaz
28
2d sin   n
 n 
1
  sin  
 2d 
Mathematical Information
Allowed reflection for cubic lattices
• Primitive h2 + k2 + l2 = 1,2,3,4,5,6,8,9,10,11,12,13,14,16…
• Body-centered h2 + k2 + l2 = 2,4,6,8,10,12,14,16…
• Face-centered h2 + k2 + l2 = 3,4,8,11,12,16,19,20,24,27,32…
• Diamond cubic h2 + k2 + l2 = 3,8,11,16,19,24,27,32…

Hexagonal close packing Cubic close packing

Top-down versus Bottom-up How does
Nanotechnology
work?

By mono single X-ray structure analysis, we can say what is
the structure we have-----------
B(Me)3 is a monomer
[Al(Me)3]2 is a dimmer

P21/n is not a standard space group. There is nothing
wrong to refine the structure in P21/n it is equivalent to
P21/c. It was better to use P21/n in the past because they
used only diagonal terms for refinement ie neglecting the
correlation between parameters. That was causing
unstable refinement in P21/c. That's not the case anymore
with the full matrix.
You'll often see Dunitz, J. D. (1979). X-ray Analysis and
the Structure of Organic Molecules, p 205–206 as a
reference for this.
However, for comparison, it's nice if everybody is using

the same unit cell setting.

Quiz 1
The Following Figure represent the powder X-ray diffraction

pattern of one types of materials:
Study Figure well and answer the following question:

How to determine the unit cell in figure by simple calculations.
Show your calculations.

Quiz 2
Q1) Fill the following table by lattice types (P, C, I, F, or R) and required rotation symmetry for each of the following Crystal
system:
Crystal System Bravais Lattices Required rotation symmetry
Cubic
Tetragonal
Orthorhombic
Hexagonal
Trigonal
Monclinic
Triclinic
44
Q2) Write the set of axial constraints(dimensions, angles) for each of the following crystal system:
Cubic
Tetragonal
Orthorhombic
Hexagonal
Trigonal
Monclinic
Triclinic
Q3) List the full meaning conveyed by the following space groups:
a) Monoclinic, P 21 /c b) Orthorhombic, I bca
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Physical Methods in Inorganic Chemistry .

Presentation · February 2014

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Dr. Mutasem Z. Bani Fwaz

Dr.Mutasem Z. Bani Fwaz

(The Bohr model for nitrogen) (The LUMO of benzene)

spin orbit coupling

You must know the following rearrangement to do that and

S ms = +1/2 J = 5/2 and 3/2 2D

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Dr. Mutasem Zaki Bani Fawaz

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‫‪Question and answer‬‬ ‫‪Question-2-:‬‬

‫‪Dr. Mutasem Zaki Bani Fawaz‬‬ ‫‪13‬‬

MS = 1/2 + 1/2 + 1/2 = 3/2 = S

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– mS = + ½ or – ½ only because the electron can either “spin” clockwise

– S = Spin Quantum Number = S mS

» Arrange the d-electrons in the 5d-orbitals as high spin

» Apply mS = g[S(S+1)]½ = 2[5/2(7/2)]½ = 5.92 Bohr

Or [n(n+2)] ½ = [5(7)] ½ = (35) ½ = 5.92

Dr. Mutasem Zaki Bani Fawaz 19

Metal ion dn configuration μeff(spin only) μeff (experimently)

Q1) The [Ni(pyridine)4(H2O)2]Br2 has d-d absorption

Q2) Calculate the spin-only magnetic moment for

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Dr.Mutasem Z. Bani Fwaz

Dr. Mutasem Z. Bani Fwaz

h5-Cp h3-Cp h3-allyl h1-allyl

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CN-, Cl-, Br-, I-, H-

3) Charged complex: [Mn(CO)6]+

4) M—M Bond: (CO)5Mn—Mn(CO)5

Dr. Mutasem Zaki Bani Fawaz 9

HOMO:highest occupied molecular orbital

Dr. Mutasem Zaki Bani Fawaz 10

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Abundance of first isotope peak M: .691 x .755 = .521

2. Rearrangement involving hydrogen migration are frequent

This rearrangement depends on readiness of metal to

Observed in: Keto-organotin: RCO (CH2)3 Sn (CH3)3

In Electron deficient compounds of group II and III (Be and Al),

The molecular mass of limonite

Q3: A 25.0 g sample of an orange compound contains 6.64 g of

a. What is the empirical formula of nicotine?

b. What is the molecular formula of nicotine?

Electron Paramagnetic Resonance