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SECTION- A
Instructors: Dr. Saroj L. Samal (Inorganic Chemistry)
Dr. Supratim Giri (Physical Chemistry)
Dr. Debayan Sarkar (Organic Chemistry)
(LA 101) (2-1-0 course)
Spectroscopy
Thermodynamics
Electrochemistry Dr. Supratim Giri
Chemical kinetics
Books:
1. Atkins’ Physical Chemistry by Peter Atkins and Julio de Paula
2. Inorganic Chemistry by Gary L. Miessler and Donald A. Tarr
Dr. Saroj L. Samal 5
Department of Chemistry
Atoms
Subatomic particles
• Two regions.
• Nucleus- protons and neutrons. (Occupies very
small space)
• Electron cloud- region where you might find
an electron. [Occupies large]
Dr. Saroj L. Samal 6
Department of Chemistry
Atomic Spectra
7
Atomic Structure
2 2
mv Ze
r 4 o r 2
𝑛2 ℎ 2
v2 = …… (1)
4π2 𝑚2 𝑟²
Increasing energy
E = −Z2e4m/8εₒ2n2h2 ……. (4)
hc Z 2 e 2 1 1
2
8 0 a0 ni n f
2
1 1 1
RH 2 2
ni n f
13
Drawbacks of Bohr model
The model only worked for hydrogen-like atoms.
The existence of fine and hyperfine structure in spectral lines.
The Zeeman effect - changes in spectral lines due to external
magnetic fields.
Could not explain why the intensity of the spectra lines were
NOT all equal.
Wave nature of electron was not considered in Bohr’s model
Constructive destructive
Interference: Superposition of two or more waves to
generate new patterns 15
de Broglie equation (1924)
(Wave-particle duality)
λ = h/mv
Q2. Calculate the de Broglie wave length of
(i) an electron moving with velocity 104 m/sec. [mass of e = 9.1 x 10−31 kg]
(ii) A 400 g Frisbee moving at 10 km/h
Ans. (i) 72 nm
(ii) 5.96 x 10-34 m (immeasurable)
Dr. Saroj L. Samal 16
Department of Chemistry
Experimental proof of de Broglie hypothesis
px x ħ/2
or ΔPx Δx ≥ h/4π
Answer
H=E
E = Total energy of electron
= wave function of electron
H = Hamilton operator
In one dimension
Ĥ = ħ2/2m d2/dx2 + V(x) Where, V(x) = potential energy, (V = − Ze2/4πor)
In three dimensions,
Ĥ = ħ2/2m (2 ψ/x2 + 2 ψ/y2 + 2ψ/z2) + V(x,y,z)
H=E
Q1. Show that eax is an Eigen function of the operator d/dx,
and find the corresponding eigenvalue.
H=E
Eigen function is the wave function of an electron corresponding to
the energy E.
2. must be continuous.
3. must be finite.
5. Probability of finding particle over the whole space must be unity (Normalization Condition)
+∞ 2
−∞
𝜓 𝑑𝜏 = 1 (𝑑𝜏 gives the volume element given by dx, dy and dz)
+∞
If ψ is a complex function,
−∞
𝜓𝜓 ∗ 𝑑𝜏 = 1
6. Condition of Orthogonality
If ψ1 and ψ2 are two acceptable wave functions, they are orthogonal.
+∞
𝜓 𝜓 𝑑𝜏 = 0
−∞ 1 2
radial
angular
Dr. Saroj L. Samal function 32
function
Department of Chemistry
Radial and Angular part of wave function
Rnl(r) r l
(Polynomial of degree n-l-1)
e-r/a0
Dr. Saroj L. Samal 33
Department of Chemistry
Radial part of wave function
2 3 ( n l 1)! 1/ 2 l 2l 1 / 2
R ( r ) [( ) ] L ( ) e
na0 2n[(n l )!]3
n 1
Rnl(r) r l …… 1
(Polynomial of degree n-l-1) …… 2
e-r/a0 …… 3
The first factor determines the behavior of the
wave function w.r.t. the distance from the nucleus
Orbital n l R(n,l)
3
1s 1 0 1 2 2
2 e
a0
3
2s 2 0 1 1 2 4
2 e
2 2 a0 2
3
2p 2 1 1 1 2 4
e
4 6 a0
3
3s 3 0 1 1 2
2 6
6 2 e
9 3 a0 9
3
3p 3 1 1 1 2 6
4 e
27 6 a0 3
Dr. Saroj L. Samal = 2r/a0 35
Department of Chemistry
2s orbital
1s orbital
n=1, l=0,
n=1, l=0, No. of nodes =1
No. of nodes =n-l-1=0
3
1 1 2 4
3 R( n,l ) (r ) 2 e
1 2 2 2 2 a0 2
R( n,l ) (r ) 2 e
a0
36
2p orbital
3s orbital
n=2, l=1,
n=3, l=0, No. of nodes =0
No. of nodes =2
3
1 1 2 4
3 R(r ) e
1 1 2
2 6 4 6 a0
R(r ) 6 2 e
9 3 a0 9
37
Radial part of wave function
4πr2R2 = The radial probability function (P). Pdr describes the probability of
finding the electron in a spherical shell of radius r and thick dr.
A radial distribution function for an orbital with QNs n and l has n-l
peaks, the outermost peak being highest.
Yl,m (θ,ϕ):
Orbital l ml Y l, ml (,)
1
s 0 0 1 2
4
p 1 0 1
3 2
cos
4
1
px 1 +1 3 2
sin cos
4
1
py 1 -1 3 2
sin sin
4
Dr. Saroj L. Samal 41
Department of Chemistry
Hydrogen atom
Ĥψ=Eψ
(ħ2/2m 2 +Ze2/r ) ψ = E ψ
Dr. Saroj L. Samal 42
Department of Chemistry
Solution of the Schrödinger wave equation
ψn,l,ml(r,,) = Rn,l(r)Yl,ml(,)
1s atomic orbital (n = 1, l = 0, ml = 0
3 1
Z 2 2 1 2
1s = 2 e 1
a0 4 1 2
Y l, ml (,) =
4
Radial part Angular part
3
Z 2 2
R n, l = 2 e
a0
3
1 Z 2 / 2 3 2 z
1
2pz = e
2 6 a0 4 r
For H atom Z = 1, so
3
1 1 2 / 2 3 2
1
2pz = e cos
2 6 0
a 4
1
1 15 2
xy Similarly the dxz, dyz
3dxy = R n, l
4 r2
Y (θ, )
1
1 15 2
x2 y 2
3dx²-y² = R n, l Since the angular part contains
4 r2 two or more variables, so these
orbitals have shapes in two
1
axial directions or more.
1 5 2
2 z2 x 2 y 2
3dz² = R n, l
4 r2
At nodal surface, = 0
either R(r) = 0
or Y(,) = 0
Angular node
Radial node
xz -plane
Ans. In nodal surfaces, Y = 0
Y = 0, when either x = 0 or y = 0
So the nodal surfaces are
x = 0 (yz plane)
and y = 0 (xz plane) yz -plane
Ans: The nodal surfaces of dxy, dyz and dzx orbitals contains the
axes and hence their lobes lie in between axes. However, the
nodal surfaces of dx2−y2 orbital are x = y and x = −y. So the lobes
of dx2−y2 lie along the axial direction.
node
z
y
dxz + ve phase
− +
x
+ − − ve phase
The angular part of dxy, dxz, dyz contain product of two component. So the product
of signs gives the sign of the lobe.
For dx²-y², the angular part contains x2−y2. so the wave function is positive along x-
direction (positive and negative) and negative along y direction.
For dz² , the angular function contains 2z2−x2−y2, so the wave function is positive
along z direction (both positive and negative) and negative in xy-plane.
Dr. Saroj L. Samal 55
Department of Chemistry
What we learn in atomic structure?
Quantum numbers.
Atomic structure
Q1. Identify the radial and angular part in the following wave functions:
ΨA = (1/πao3)1/2 exp-(r/ao)
Orbitals Radial
nodes
Ans 2. 1s 0
2s 1
The number of radial nodes = n – l - 1 3s 2
6s 5
The number of angular nodes = l (orbital quantum number) 2p 0
3p 1
For any atomic orbital, total number of nodes = n - 1 3d 0
4d 1
5d 2
4f 0
Q3. Calculate the magnitude of the orbital angular momentum of 3d orbital.
Note: that I is a vector quantity, its magnitude is given above but it has certain
orientations and that too are quantized.
Q4. What are the nodal surfaces of 3dx2−y2 orbital. Draw the atomic orbital and
explain the sign of each lobe.
Ans. The nodal surfaces are the surfaces where the wave
function becomes zero.
So, 3dx²-y² = 0, when x2−y2 = 0
x=y
or, x = −y
Hence the nodal surfaces are x = y and x = −y planes
Sign of lobes
For dx²-y², the angular part contains x2−y2, which is always
positive along x direction. Because x >> y in the lobe along
x direction. Similarly one explain that x2−y2 will be
negative in the lobes along y direction.
61
5. What are the significance of the two quantum numbers n and l ?
6. Can you illustrate the difference between electron density and radial
probability distribution for Ψ1S of hydrogen atom?
4.
Significance of quantum numbers
Q no. Allowed values Functions
By definition,
Probability density [P(r)] = |Ψ1s|2 = [exp (-2r/ao)]/πao3
Plot of Plot of
probability density vs r radial distribution vs r
|Ψ1s|2 4 πr2
|Ψ1s|2
r/a
r/ao r/ao
65
Additional explanation for more inquisitive students:
To understand radial node, we have to first understand probability distribution
of electron in hydrogen atom.
radial node!