Atomic STR - CY1101 - SLS PDF

Welcome to CY1101 (general chemistry) class
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)
Mon 4:15-5:15 Teaching class

Tue 4:15-5:15 Teaching class
Thu 4:15-5:15 Tutorial class
1
The Scope and Objective
CY1101 (General Chemistry)
The course provides a comprehensive survey of the concepts involved in

the study of the
 Electronic structure of atoms

 Chemical bonding Dr. Saroj L Samal
 Coordination chemistry
 Spectroscopy
 Thermodynamics
 Electrochemistry Dr. Supratim Giri
 Chemical kinetics
 Organic reaction mechanism. Dr. Debayan Sarkar
Dr. Saroj L. Samal 2

Department of Chemistry
CY1101 (General Chemistry)
Mark distribution
Mid sem- 30 marks
End sem- 50 marks
Teacher Assessment (TA)- 20 marks
(TA marks will depend on one quiz written test,
attendance and discipline of the student in the class.)
Class attendance is very important.

If one has > six absents then he will have one grade back
> 12 absents then he/she will be debarred (failed).
Absence in any class-- you may loose some marks in exam.

Books:
1. Inorganic Chemistry by Gary L. Miessler and Donald A. Tarr
2. Atkins’ Physical Chemistry by Peter Atkins and Julio de Paula
3. Fundamentals of molecular spectroscopy, C. N. Banwell,E. N. McCash,
1994.
4. Organic Chemistry, Clayden, Greeves, Warren and Wothers, Oxford,
2001.
5. Principles of physical Chemistry, B. R. Puri, L. R. Sharma, M. S.
Pathania, 2001.

Chapter 1. Electronic structure of atomic
Atomic structure: Overview of Bohr’s atomic model,

Schrodinger wave equation, Interpretation of wave function
(radial and angular), Hydrogen like atom, Concept of atomic
orbitals.
Books:
1. Atkins’ Physical Chemistry by Peter Atkins and Julio de Paula
2. Inorganic Chemistry by Gary L. Miessler and Donald A. Tarr
Atoms
Subatomic particles
Name Symbol Discovered by, year

Electron e- J. J. Thomson, 1897
Nucleus n+ p E. Rutherford, 1911
Proton p+ H.G.J. Moseley, 1913
• Two regions.
• Nucleus- protons and neutrons. (Occupies very
small space)
• Electron cloud- region where you might find
an electron. [Occupies large]
Atomic Spectra
7
Atomic Structure
Bohr’s Model (planetary Schrödinger Model (electron

model)-1914 cloud model)- 1926
Assumes electron as particle Assumes electron as wave
Got Nobel Prize in 1922 for Got Nobel Prize in 1933

foundational contribution to for his Schrödinger wave
understand atomic structure. equation for H-like atoms.

Bohr model of hydrogen-like atom
1. The electrons moves around the nucleus in a well defined

circular orbits, which are distinctly separated from each other. The
centipetal force that curves the path of the electron is provided by
the columbic force of attraction between them
2 2
mv Ze

r 4 o r 2

2. The total energy of the electron remains constant as long as it

remains in the orbit
Etotal  K .E.  P.E.
1 2  Ze2 
 mv    
2  4 0 r 
3. Only certain orbits are allowed. Each orbit having a

quantized value of angular momentum
mvr = nh/2 (n = 1,2,3,….)

mvr = nħ
The orbits are discrete, so the energy of an electron in an orbit is

quantized.
mvr = nh/2π
𝑛2 ℎ 2
v2 = …… (1)
4π2 𝑚2 𝑟²
The electrostatic attraction between electron and nucleus must be

equal to centrifugal force.
𝑚𝑣2 𝑍𝑒 2 𝑍𝑒 2
=  v2 = ……….. (2)
𝑟 4πεₒ𝑟2 4πεₒ𝑚𝑟
Combining (1) and (2)

r = εon2h2/πme2Z …….. (3)
Dr. Saroj L. Samal
r = 0.529 Å = First Bohr’s radius for H-atom 11
Bohr’s Model ∞ 0.00 eV
The energy of an electron when it jumps 5 −0.54 eV

from one orbit to other is 4 −0.85 eV
3 −1.51 eV
E = −1/2mv2, E = −Ze2/8πεₒr
By putting the value of r in the above equation, 2 −3.4 eV
Increasing energy
E = −Z2e4m/8εₒ2n2h2 ……. (4)
Or, E = −Z213.6/n2 eV ….… (5)

m = mass of electron 1 −13.6 eV
Z = Charge of nucleus or atomic number
e = electronic charge
h = Planck’s constant
n = principal quantum number
Q1. What is the ratio of the energy of a ground state He+
ion to that of Be3+ ion?
 Explains Line spectra of hydrogen atom
h  E f  Ei
Z 2e 2 Z 2e 2
h   
8 0 a0 n f 8 0 a0 ni2
2
hc Z 2 e 2  1 1 
  2
 8 0 a0  ni n f 
2
1  1 1 
   RH  2  2 
  ni n f 
 Calculated the Value of Rydberg Constant (R).
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
Information gained from Bohr’s model

It provide foundation to understand atomic structure.
The total energy of electron in H-atom it predicts is exactly agree with

these obtained from Schrodinger equation (discussed later).
Wave-Particle Duality
Common concept of particle in nature: electrons, Light (photoelectric

effect)
Common concept of wave: diffraction, interference; again exhibited by
Light!!!!
Constructive destructive
Interference: Superposition of two or more waves to
generate new patterns 15
de Broglie equation (1924)
(Wave-particle duality)
Just as light exhibits both ‘wave-like’ (diffraction), and

‘particle-like’ characteristics, so should all material objects.
The wave length of a particle moving with a velocity ‘v’ is

given by:
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)
Experimental proof of de Broglie hypothesis
Davisson–Germer experiment (1923-1927) confirms the de Broglie

hypothesis (wave-particle duality).
They discovered the wave nature of electron by getting a diffraction

pattern from a Ni crystal by bombarding a beam of electron.

Heisenberg’s uncertainty principle (1927)
It is impossible to specify simultaneously, with arbitrary

precision, the momentum and position of a microscopic
particle.
px x  ħ/2
or ΔPx Δx ≥ h/4π

Heisenberg’s uncertainty principle
(Concept of orbital)
 The energy of spectral line is
measured with great accuracy, and
hence the energy of electron.
 Precision in energy  Precision in

IR
momentum
 So there is large uncertainty in Visible
the location of electron.
 Hence orbits are replaced by
orbitals (the probability of finding UV
an electron in a given space).
 Orbitals are described by wave

functions.
Q3. Suppose the speed of a projectile of mass 1.0 g is known to
within 1 μm/sec. Calculate the minimum uncertainty in its position.
Answer
The minimum uncertainty in position is Δx = h/4πmΔv
Putting all the values, we get Δx = 5x10−26 m
The uncertainty is completely negligible for all practical purposes concerning

macroscopic objects. However, if the mass is that of an electron, then the same
uncertainty in speed implies an uncertainty in position far larger than the
diameter of an atom (the analogous calculation gives Δx = 60 m). So the concept
of a trajectory for a microscopic object, the simultaneous possession of a precise
position and momentum, is untenable.
Dr. Saroj L. Samal

Schrödinger's equation
The Schrödinger equation describes the wave properties of an
electron in terms of position, mass, energy.
The simplest form of time independent Schrodinger equation:
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 = − Ze2/4πor)
In three dimensions,
Ĥ = ħ2/2m (2 ψ/x2 + 2 ψ/y2 + 2ψ/z2) + V(x,y,z)
Dr. Saroj L. Samal [−h2/8π2m 2 +V]  = E  21

Understanding the Schrödinger equation
(Hamiltonian operator) (Eigenfunction) = (Eigenvalue) (Eigenfunction)
H=E
Q1. Show that eax is an Eigen function of the operator d/dx,
and find the corresponding eigenvalue.
Q2. Show that eax² is not an Eigen function of d/dx.

d/dx(eax²) = 2ax (eax²)
This is not an Eigen value even though the same function

occurs on the right, because the function is now multiplied by
a variable factor (2ax), not a constant factor.
Understanding the Schrödinger equation
(Hamiltonian operator) (Eigenfunction) = (Eigenvalue) (Eigenfunction)
H=E
 Eigen function is the wave function of an electron corresponding to
the energy E.
 Eigen function is different for each eigenvalue.
 By solving Schrödinger equation one can find the wave functions

(eigenfuncctions) and the corresponding allowed energies
(eigenvalues).

Solutions of Schrödinger equation
[−h2/8π2m 2 +V]  = E 
There are many solutions to the above equation. However, the acceptable
solutions must satisfy following conditions.
1.  must be single valued.


2.  must be continuous.
3.  must be finite.

Solutions of Schrödinger equation
4. First derivative of  w.r.t. its variables must be continuous.
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

 For an atom several wave functions (1, 2, 3) will satisfy
these conditions and each of these has a corresponding energy
(E1, E2, E3)
 The wave function of the electron in the hydrogenic atom is called

an atomic orbital. An orbital is a one-electron wave function.
 Each orbital is described uniquely by a set of three quantum

numbers, n, l, ml.

Quantum Numbers
There are four quantum numbers.
Orbital is defined by three quantum numbers (n, l, ml).
An electron is defined by four quantum numbers (n, l, ml, ms).
Principal quantum number (n):

Determines the total energy of an electron.
E = −1/n2 (Z2e4μ/8εₒ2h2)
Or, E = 1/n2 (−13.6) eV
Has value 1, 2, 3, …………∞

Quantum Numbers
Q. Why the value of ‘l’ is always less than ‘n’?

Magnetic quantum number (ml):
Describe orientation of orbital in space.
It is the z-component of angular momentum.
(so it never be larger than the ‘l’ value)
It may have +ve z-component or
–ve z-component
So the value ranges from –l, ……0, …….+l
Quantum Numbers
Spin quantum number (ms):

Describes orientation of electron spin in a magnetic field.
The value of ms either +1/2 (in the direction of the field)

or −1/2 (opposed to it).
Arises due to spinning of electron.

Understanding of the Wave Function
ψ does not have any physical significance.
ψ2 or (ψ ψ* ) has a meaningful significance.
It is interpreted as a measure of density of electron at that point

Parallel to the concept of intensity as square of amplitude in light
The Born Interpretation
𝜓2𝑑𝜏 is considered as a measure of probability of finding the

particle in the small volume 𝑑𝜏 (= dx.dy.dz)

Radial and Angular part of wave function 
In 3D,  may be expressed either in Cartesian coordinates

(x,y,z) or in spherical coordinates (r,θ,ϕ).
r = represents the distance from the nucleus.

θ = is the angle from z-axis, it varies from 0-π.
ϕ = is the angle from x-axis, it varies from 0-2π.
(x,y,z) can be converted to (r,θ,ϕ) using:

x = r sinθ cosϕ
y = r sinθ sinϕ
z = r cosθ

The Schrödinger equation in spherical polar coordinate is
h2  1   2   1     1  2  e2
  2 r  2  Sin  2 2 2
   E
2me  r r  r  r Sin     r Sin    4 0 r
 may be separated into radial component and two angular

components.
(r,θ,ϕ) = R(r) (θ ) (ϕ)
Combining the two angular components
(r,θ,ϕ) = Rn,l(r) Yl,m(θ,ϕ)
radial
angular
Dr. Saroj L. Samal function 32
function
The radial function, Rn,l(r) :
The radial function is determined by the quantum numbers n

and l.
2 3 (n  l  1)! 1/ 2 l 2l 1  / 2
R(r )  [( ) ]  Ln 1 (  ) e
na0 2n[(n  l )!]3
2r

a0
Rnl(r)  r l
 (Polynomial of degree n-l-1)
 e-r/a0
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
 the second factor determines the number of

nodes =(n-l-1)
 the third ensures that the function goes to 0 as r  

2 3 ( n  l  1)! 1/ 2 l 2l 1
R ( r )  [( ) ]  Ln 1 (  )e   / 2
na0 2n[(n  l )!] 3
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
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 Probability 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.
For any shape, P = r2R2
Maximum correspond to distance from nucleus at which

the electron has highest probability of being found.

A radial distribution function for an orbital with QNs n and l has n-l
peaks, the outermost peak being highest.

Angular part of wave function 
ψ(r,,) = R(r) ()() = Rn,l(r) Yl,ml(,)
Yl,m (θ,ϕ):
The angular function is determined by the quantum numbers

l and ml.
The angular function, Yl,m(θ,ϕ), describes shape of the

orbitals and their orientation in space.

Angular part of wave function 
ψ(r,,) = R(r) ()() = Rn,l(r) Yl,ml(,)
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 
Hydrogen atom
Hydrogen has special significance

•No approximation is required in solution of Schrödinger equation
•Can get expression for energy levels
For H atom the Schrödinger wave equation can be written as
Ĥψ=Eψ
(ħ2/2m 2 +Ze2/r ) ψ = E ψ
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 
 It is a constant and does not depend on  and 
 S-orbitals are spherically symmetrical

2p atomic orbitals (n = 2, l = 1, ml = +1, 0, −1
3
1  Z  2  / 2  3  2  z 
1
 2pz =    e    
2 6  a0   4   r 
Radial part (R n, l) Angular part (Y l, ml (,))
Note: Z is the atomic number and z is the z-direction/component
In polar coordinate the above equation becomes

3
1  Z  2   / 2 3  2
1
 2pz =    e   cos  (Since, z = r cosθ)

2 6  a0   4 
2p atomic orbitals (n = 2, l = 1, ml = +1, 0, −1
For H atom Z = 1, so
3
1  1  2   / 2 3  2
1
 2pz =    e   cos 
2 6 0
a  4 
 The angular variation of wave function depend

on cos .
 The probability density is proportional to cos2.
 The probability density has maximum value
along an arbitary axis (z-axis) on either side of the
nucleus ( at = 0 and 180o)
2p atomic orbitals
Similarly the wave functions (real part of wave functions) of
other two p-orbitals are given below:
3
1  1  2  / 2  3  2
1
 2px =    e   sin  cos  (Since, x/r = sinθcos)

2 6  a0   4 
3
1  1  2   / 2 3  2
1
 2py =    e   sin  sin  (Since, y/r = sinθsin)

2 6  a0   4 

3d atomic orbitals (n = 3, l = 2, ml = +2, +1, 0, −1, −2)
(dxy, dxz, dyz, dx²-y², dz²)
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

Nodal surface(s) of atomic orbitals
node
Nodal surface is a surface with zero electron density.
Nodes appear naturally as a result of the wave nature of the electron
At the nodal surface the wave function changes its sign.
At nodal surface,  = 0
either R(r) = 0
or Y(,) = 0
Angular node
Radial node

Angular nodal surface
If Y(,) = 0, angular nodes result.

Angular node
Angular nodes are planar or conical.
Number of angular nodes = l
Orbital No. of angular nodes

s- orbital 0
p-orbital 1
d-orbital 2
f-orbital 3

Radial or Spherical nodal surface
If R(r) = 0, radial nodes or spherical nodes result.
Number of radial nodes = n−l −1
Orbital Radial Orbital Radial Orbital Radial

nodes nodes nodes
1s 0 2p 0 3d 0
2s 1 3p 1 4d 1
3s 2 4p 2 5d 2
Radial node

Q. Describe the angular nodal surfaces for a 3dxy orbital, whose
angular wave function is
1
1  15  2
xy
Y = 4  
  r2
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

Q. Why the lobes of dxy, dyz and dzx orbitals are in between
axes and the lobes of dx2−y2 is along the axes?
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.

Q. Describe the spherical nodal surface of 2s orbital of hydrogen
atom. The radial component of 2s atomic orbital is:
3
1  1  2    4 (ρ = 2Zr/ao)
R( 2 s ) (r )     2  e
2 2  a0   2
node

Sign of atomic orbital
Sign of lobes does not mean electronic charge.
It represents the phase/direction of wave function.
Atomic orbital along positive axial direction has a positive sign

and negative axial direction has a negative sign.
z
y
dxz + ve phase
− +
x
+ − − ve phase

Sign of atomic orbital
The angular part of s-orbitals contain constant value, no variables. So there is no
change in sign.
The angular part of p-orbital contains either x or y or z. Since the x, y, or z direction

may be positive or negative, so the wave function along positive axis has a positive
sign and along negative axis has negative sign.
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.
What we learn in atomic structure?
 Bohr’s model of atomic structure.
 de Broglie equation, Heisenberg’s uncertainty principle.
 Schrodinger atomic model or wave equation.
 Quantum numbers.
 Solutions (only wave function part) of Schrodinger equation.
 Nodal surfaces and sign of atomic orbitals.

Tutorial
Atomic structure
Q1. Identify the radial and angular part in the following wave functions:
ΨA = (1/πao3)1/2 exp-(r/ao)
ΨB = 1/8(2/πao3)1/2 (r/ao) exp-(r/2ao) Sinθ exp(-iΦ)
Ans 1. Radial part has been marked RED.
ΨA = (1/π) ½ (1/ao)3/2 exp-(r/ao)
ΨB = 1/8(2/ao3)1/2 (r/ao) exp-(r/2ao) (2/π)1/2Sinθ exp(-iΦ)

Q2. Find the total number of nodes (nodal surfaces) and the number of radial
(spherical) nodes in the following orbitals.
2p, 3s, 4d, 4f, 5p
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.
Orbital angular momentum:
Electrons orbiting around nucleus have quantized orbital angular momentum

Angular momentum = √[l(l+1)] ħ Where l = 0,1,2,3…. etc
For 3d orbital, l value is 2 : the magnitude is √6ħ
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
n (principal) 1,2,3…………… energy & size of orbital
l (orbital/azimuthal) (n-1),(n-2)…. 0 shape & angular momentum
m (magnetic) ±l, ±(l-1),…….0 direction & behavior under magnetic field

s (spin) +1/2, -1/2
axial angular momentum due to spin of e-
6.
Ψ1s = (1/πao3)1/2 exp-(r/ao)
By definition,
Probability density [P(r)] = |Ψ1s|2 = [exp (-2r/ao)]/πao3
Radial probability distribution = f(r) = P(r)× 4πr2 = [exp (-2r/ao)]/πao3 × 4πr2
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.
Ψ1s = Ψ100 = (1/πao3)1/2 exp-(r/ao)
The probability of finding an electron at a particular point Ξ |Ψ1s|2
|Ψ1s|2 = [exp (-2r/ao)]/πao3 = probability density funtion P(r)
Plotting the above P(r) vs r we get:
Probability density is highest at a place nearest to the nucleus!
When r → 0, volume → infinitesimally small
But we all know that the total amount of e- cloud is negligible

within the small volume of nucleus.
So probability density does not give the accurate

picture of e- cloud distribution!
Radial probability distribution function:
We should better ask a smarter question: how much e- cloud
is contained within a spherical shell of thickness dr?
r r + dr
Answer= probability density × shell volume
r
Shell volume = P(r)× 4πr2dr = f(r)dr [f(r) is radial dist. funct.]
= 4πr2dr
f(r)1s (hydrogen atom) = [exp (-2r/ao)]/πao3 × 4πr2
or, ao3/4f(r) = r2 exp (-2r/ao)
The radial distribution function is maximum

When r = ao for hydrogen atom!
3
For H2 atom, ao = 0.53 Å!

Radial distribution function of s orbitals:
Definition: the total probability of finding an electron in a spherical shell of infinitesimally
small volume of dv
radial node!

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Welcome to CY1101 (general chemistry) class

Mon 4:15-5:15 Teaching class

The course provides a comprehensive survey of the concepts involved in

 Electronic structure of atoms

 Organic reaction mechanism. Dr. Debayan Sarkar

Dr. Saroj L. Samal 2

Class attendance is very important.

Absence in any class-- you may loose some marks in exam.

Dr. Saroj L. Samal 4

Atomic structure: Overview of Bohr’s atomic model,

Name Symbol Discovered by, year

Nucleus n+ p E. Rutherford, 1911

Proton p+ H.G.J. Moseley, 1913

Bohr’s Model (planetary Schrödinger Model (electron

Got Nobel Prize in 1922 for Got Nobel Prize in 1933

Dr. Saroj L. Samal 8

1. The electrons moves around the nucleus in a well defined

Dr. Saroj L. Samal 9

2. The total energy of the electron remains constant as long as it

3. Only certain orbits are allowed. Each orbit having a

mvr = nh/2 (n = 1,2,3,….)

The orbits are discrete, so the energy of an electron in an orbit is

The electrostatic attraction between electron and nucleus must be

Combining (1) and (2)

The energy of an electron when it jumps 5 −0.54 eV

By putting the value of r in the above equation, 2 −3.4 eV

Or, E = −Z213.6/n2 eV ….… (5)

 Calculated the Value of Rydberg Constant (R).

Information gained from Bohr’s model

The total energy of electron in H-atom it predicts is exactly agree with

Common concept of particle in nature: electrons, Light (photoelectric

Just as light exhibits both ‘wave-like’ (diffraction), and

The wave length of a particle moving with a velocity ‘v’ is

Davisson–Germer experiment (1923-1927) confirms the de Broglie

They discovered the wave nature of electron by getting a diffraction

Dr. Saroj L. Samal 17

It is impossible to specify simultaneously, with arbitrary

Dr. Saroj L. Samal 18

 Precision in energy  Precision in

 Orbitals are described by wave

The minimum uncertainty in position is Δx = h/4πmΔv

Putting all the values, we get Δx = 5x10−26 m

The uncertainty is completely negligible for all practical purposes concerning

Dr. Saroj L. Samal

Dr. Saroj L. Samal [−h2/8π2m 2 +V]  = E  21

(Hamiltonian operator) (Eigenfunction) = (Eigenvalue) (Eigenfunction)

Q2. Show that eax² is not an Eigen function of d/dx.

This is not an Eigen value even though the same function

(Hamiltonian operator) (Eigenfunction) = (Eigenvalue) (Eigenfunction)

 Eigen function is different for each eigenvalue.

 By solving Schrödinger equation one can find the wave functions

Dr. Saroj L. Samal 23

1.  must be single valued.

Dr. Saroj L. Samal 24

Dr. Saroj L. Samal 25

 The wave function of the electron in the hydrogenic atom is called

 Each orbital is described uniquely by a set of three quantum

Dr. Saroj L. Samal 26

Orbital is defined by three quantum numbers (n, l, ml).

An electron is defined by four quantum numbers (n, l, ml, ms).

Principal quantum number (n):

Dr. Saroj L. Samal 27

Q. Why the value of ‘l’ is always less than ‘n’?