CURAJ Quantum Chemistry An Introduction

Quantum chemistry
An introduction
References
Chapter 8: Physical chemistry by P. W. Atkins
Chapter 1: Physical chemistry by D. A. Mcquarrie
Chapter 1: Quantum chemistry by I. N. Levine
Chapter 4: The chemistry maths book by Steiner
Several figures and tables are taken from the first two books
Advances in basic sciences in 19th century:
Chemistry
Atomic weight
3 Dalton, Avogadro
7 Berzelius, Dumas
Stanislao reconsidered Avogadro law after 50

Cannizzaro years
Sunto di un corso di filosofia chimicu
fatto nella Reale Università di Genova,
Nuovo cimento, 7 (1858), 321
Karlsruhe congress 1860, Germany
https://www.sciencehistory.org/historical-profile/stanislao-cannizzaro
https://www.encyclopedia.com/people/science-and-technology/chemistry-
biographies/stanislao-cannizzaro
Chemistry
Reproduced from https://corrosion-doctors.org/Periodic/Periodic-Mendeleev.htm

Further reading https://www.encyclopedia.com/people/science-and-technology/chemistry-
biographies/dmitrii-ivanovich-mendeleev
Chemistry
Structure Reactivity
August Kekule S. Arrhenius
−Ea
k = Ae RT
taken from: https://commons.wikimedia.org/w/index.php?curid=29661966
taken from: Physical chemistry: P. Atkins and J. de Paula
Physics
Classical Thermodynamics Electrodynamics
mechanics
J. Joule:
I. Newton Equivalence of
d ∂T ∂V heat and energy
+ = 0
dt ∂ ẋ ∂x S. Carnot:
Entropy J. C. Maxwell
C. J. Lagrange J. Gibbs: Is light a particle
d ∂L ∂L Formulation of or wave?
− = 0 Thermodynamics
dt ∂ ẋ ∂x Double slit
Most relevant for experiment
W. Hamilton chemistry
https://commons.wikimedia.org/w/index.php?curid=2107870
https://www.youtube.com/watch?v=Yf 4Qv-A55Q
Failure of classical physics: Blackbody radiation
EM Radiation How we see color
Iron Black body radiation
http://www.webexhibits.org/causesofcolor/3.html
Rayleigh-Jeans Law:
8πkB T 2
ρν (T )dv = ν dν
c3
Plank theory: Energy values are discrete and
proportional to an integral multiple of the frequency
E = nhν
8πh ν 3 dν
ρν (T )dν =
c3 e khν
BT − 1
h = 6.626 × 10−34 J s
R = 8.314 J K-1 mol-1
NA = 6.023 × 1023 mol-1
c = 3.0 × 108 m s-1
R
kB = = 1.3806 × 10−23 J K-1
NA
What are the units of ρν (T )dν
Js s-3 s-1
=
J s s-1
= J m-3
(m s-1 )3
e J K-1 K −1
Failures of classical physics: Heat capacities
Dulong-Petit law: The molar heat capacities of all
monatomic solids are the same and (in modern units) close
to 25 J K-1 mol-1
Equipartition theorem: The mean energy of an atom as it
oscillates about its mean position in a solid is kT for each
direction of displacement.
∂U
U = 3N kT = 3RT → CV = = 3R = 24.9 J K-1 mol-1
∂T
Einstein theory:
Failure of classical physics: Photoelectric effect
I The Kinetic energy of electrons does not depend on

Intensity
I For electron ejection, the frequency of light (ν) should
be greater than a threshold frequency (ν0 )
1 2
KE = mv = hν − W
A. Einstein 2
W = hν0
Evidence for quantization: Atomic spectra
EM Radiation
https://cnx.org/contents/5IbdLw3l6/Bohr-s-Model-of-the-Hydrogen-Atom
Evidence for quantization: Hydrogen spectrum

Rydberg formula 1 1
ν̄ = RH 2
− 2
n1 n2
RH = 109677.5 cm-1
Spectroscopic transitions:
1s → 2s
1s → 2p ..... etc
Evidence for quantization: Molecular spectrum
Electronic spectrum of Quantization

SO2
∆E = hν (1)
Wave particle duality: Louis de Broglie
wavelength
Particle Wave
Wave particle duality

If light can show duality, then matter can also show duality
de Broglie h
wavelength λ=
mv
https://www.youtube.com/watch?v=Yf 4Qv-A55Q
de Broglie wavelength: Cricket ball
Jasprit Bumrah clocked 153kmph speed in an IPL match.
Considering the weight of a cricket ball as 150 gm,
calculate the de Broglie wavelength associated with it?

1.0
v = 153kmph = 153 × 10 m × 3
s−1 = 42.5 m s-1
3600
m = 150 gm = 150 × 10−3 kg
h 6.625 × 10−34 J s
λ = =
mv 150 × 10−3 kg × 42.5 m s-1
1 2
E = mv ⇒ J = kg m2 s-2
2
6.625 × 10−34 kg m2 s-2 s
λ = −3 -1
= 0.001039 × 10−31 m
150 × 10 kg × 42.5 m s
= 1.039 × 10−34 m
Too small to detect
Large mass
de Broglie wavelength: Electron
Calculate the de Broglie wavelength of an electron traveling
at 1% speed of light?
c = 3.0 × 108 m s-1
1
v = 1% of c = 3.0 × 108 × m s-1 = 3.0 × 106 m s-1
100
m = 9.109 × 10−31 kg
h 6.625 × 10−34 J s
λ = =
mv 9.109 × 10−31 kg × 3.0 × 106 m s-1
6.625 × 10−34 kg m2 s-2 s
λ = = 0.2424 × 10−9 m
9.109 × 10−31 kg × 3.0 × 106 m s-1
= 2.424 × 10−10 m
Though small, this is comparable to interatomic distances
Profound impact on chemical understanding
de Broglie wavelength: Experimental proof
X-ray Electrons
Bohr theory
e2 mv 2
4π0 r2
= r
3 Electron revolve around a stationary state

3 The de Broglie wavelengths of the electrons in these
orbits must match or in phase
h nh
2πr = nλ ⇒ 2πr = n mv ⇒ mvr = 2π
= n~
n = 1, 2, 3etc.
http://marinersight.blogspot.com/2018/03/centrifugal-force-and-centripetal-force.html
Bohr theory
me4

1
En = −
820 h2 n2
me4

1 1
∆E = En2 − En1 = − − 2
820 h2 2
n2 n1
ν̄ = ν/c ⇒ E = hcν̄
me4

1 1
∆ν̄ = − −
820 ch3 n22 n21

1 1
= RH −
n21 n22
Hydrogen spectrum
Commonly encountered symbols and their units
Quantity Symbol Definition Unit Dimension
Length l − m L
2
Area A A∝l m2 L2
3
Volume V V ∝l m3 L3
Mass m − kg M
Time t − s T
Temperature T − K Θ
Avogadro No. NA − mol N
Velocity v v = dx
dt
m s-1 L T-1
Accelaration a a = dv
dt
m s-2 L T-2
Force F F = ma kg m s-2 M L T-2
Pressure P P =A F
kg m-1 s−2 M L-1 T-2
Dimension analysis
Ideal gas equation P V = nRT
1. Both sides of the equation must have the same
dimension
2. Sum or subtraction possible only between same
dimension
3. The arguments of function (such as exponential and
trigonometric) should be dimensionless
1
x = vt + at2
2
[x] = L; [t] = T
dx [x] d2 x [x]
[v] = = = LT-1 ; [a] = 2 = 2 = LT-2
dt [t] dt [t]

1
[x] = [v] [t] + [a] [t]2 ; L = LT-1 T + LT-2 T2
2
https://phys.libretexts.org
Dimension analysis
at2
Check whether the equation v = sin x dimensionally consistent?
The arguments of a trigonometric, exponential, logarithmic

etc has to dimensionless.
[a] = LT-2 ; [t] = T; [x] = L
[a] [t]2 LT-2 T2
2
at
= = =1 3
x [x] L
Now check the dimension of the total equation
2
at
[v] = sin ⇒ LT-1 = 1 7
x
How to make this equation dimension consistent?
2
at
v = v0 sin with v0 having same dimensions as v
x
Dimension analysis
Using the dimensions/units of ν, h, kB , c and T , find the units of radiation
energy density from Plank´s blackbody radiation equation?
8πh ν 3 dν
ρν (T )dν =
c3 e khν
BT − 1
h = 6.626 × 10−34 J s
R = 8.314 J K-1 mol-1
NA = 6.023 × 1023 mol-1
c = 3.0 × 108 m s-1
R
kB = = 1.3806 × 10−23 J K-1
NA
What are the units of ρν (T )dν
Js s-3 s-1
=
J s s-1
= J m-3
(m s-1 )3
e J K-1 K −1
Some important constants:
Taken from Atkins physical chemistry

Some important constants:
Taken from Atkins physical chemistry

Mathematics session I:
In Quantum chemistry, we use solve Schrödinger equation,
to obtain eigen functions (Ψ, wavefunction) and eigenvalues
(E, energies).
Examples HΨ = EΨ
−h2 d2

H = for 0 ≤ x ≥ l
8π 2 m dx2
−h2
2
d
H = + ∞ for x < 0 and x > l
8π m dx2
2
−h2
2
d 1
H = 2 2
+ kx2
8π m dx 2
The wavefunction (Ψ) has to be well defined to use it in
Qunatum mechanics
Chapter 4- Differentiation: The chemistry Maths book by

Steiner
Mathematics session I: Limits
2
−4
Let xx−2 be a function which we intended to use it as a
wavefunction (Ψ), we need to know
1. Is the function continuous ?
2. Is it finite valued ?
3. Is it differentiatable ?
x2 − 4 (x + 2)(x − 2)
lim = lim = lim (x + 2) = 4 if x 6= 2
x→2 x − 2 x→2 x−2 x→2
0
= if x = 2
0
2 −4
The indeterminate value 00 of the function xx−2 at x = 2
makes it difficult to use the function as wavefunction. By
2 −4
defining xx−2 = 4 for x = 2, we can make the function
acceptable
Mathematics session I: Continuity
|x|
Consider the function x
|x| x
lim+ = =1
x→0 x x
|x| −x
lim = = −1
x→0− x x
Mathematics session I: Derivatives
Derivative of a function f (x) at a point is the rate of
change of the function with respect to the variable x.

df f (x + h) − f (x)
= lim
dx h→0 h
d d d
a = 0 af (x) = a f (x)
dx dx dx
d n d d
x = nxn−1 f (x)g(x) = f (x) g(x)
dx dx dx
d d
sin x = cos x +g(x) f (x)
dx dx
d d f (x) g(x) dx d
f (x) − f (x) d
g(x)
cos x = − sin x = dx
dx dx g(x) g(x)2
d x d d d
e = ex f (z) = f (z) z
dx dx dz dx
d 1
ln x =
dx x
d n
x = nxn−1
dx
d d
d f (x) g(x) dx
f (x)− f (x) dx
g(x)
=
dx g(x) g(x)2
d d sin x cos x cos x − sin x(− sin x) 1

tan (x) = = 2
=
dx dx cos x cos x cos2 x
2
= sec x
d du dv dw
au(x) + bv(x) + cw(x) = a + b + c
dx dx dx dx
Differentiate y = 2x3 + 3ex − 21 ln x

d d
f (x)g(x) = f (x) g(x)
dx dx
You might have seen the shapes of orbitals 2px , 2py and 2pz
orbitals in your XII or in BSc. Have you ever questioned
why they are pictured as shown. In this course, you will see
the rationale or mathematics behind them. The shapes are
obtained from the following mathematical functions
5/2
1 Z
2pm = √ re−Zr/2a Ylm (θ, φ)
2 6 a
where n = 2, l = 1, m = −1, 0, 1
2
m 2l + 1 (l − |m|)! |m|
Yl (θ, φ) = Pl (cos(θ))eimφ
4π (l + |m|)!
|m| 1 dl+|m|
Pl (w) = l (1 − w2 )|m|/2 l+|m| (w2 − 1)l
2 l! dw
Derive the mathematical expressions by setting (a)l=1,m=0
(b)l=1,m=-1 and (c)l=1,m=+1
a) l = 1, m = 0
l+|m|
|m| 1 2 |m|/2 d
Pl (w) = l
(1 − w ) l+|m|
(w2 − 1)l
2 l! dw
1+|0|
|0| 1 2 |0|/2 d
P1 (w) = (1 − w ) (w2 − 1)1
21 1! dw1+|0|
1 d 1
= (1 − w2 )0 (w2 − 1) = 2w = w
2 dw 2
2
2l + 1 (l − |m|)! |m|
Ylm (θ, φ) = Pl (cos(θ))eimφ
4π (l + |m|)!
2
2(1) + 1 (1 − |0|)! |0|
Y10 (θ, φ) = P1 (cos(θ))ei0φ
4π (1 + |0|)!
2
3
= cos (θ)
4π
a) l = 1, m = −1
l+|m|
|m| 1 2 |m|/2 d
Pl (w) = (1 − w ) (w2 − 1)l
2l l! dwl+|m|
1+|−1|
|−1| 1 2 |−1|/2 d
P1 (w) = 1
(1 − w ) 1+|−1|
(w2 − 1)1
2 1! dw
2
1 d
= (1 − w2 )1/2 2 (w2 − 1)
2 dw
1
= (1 − w2 )1/2 2 = (1 − w2 )1/2
2
2
2.1 + 1 (1 − |1|)! |−1|
Y1−1 (θ, φ) = P1 (cos(θ))ei.−1.φ
4π (1 + |1|)!
2 2
3 0! 3
Y1−1 (θ, φ) = 2
(1 − cos (θ)) e 1/2 −iφ
= sin (θ)e−iφ
4π 2! 8π
2
3
Y11 (θ, φ) = sin (θ)eiφ
8π
In chapter 4, we will solve ”simple Harmonic Oscillator”
problem. The wavefunctions for the oscillator are Hermite
polynomials. The determining equations are given as
follows
α 1/4 2
Ψn (x) = (2n n!)−1/2 e−αx /2 Hn (α1/2 x)
π
n −z 2
2d e
Hn (z) = (−1)n ez
dz n
Calculate Ψ0 (x), Ψ1 (x), Ψ2 (x)
z = α1/2 x → dz = α1/2 dx
n −αx2
1/2 n αx2 d e
Hn (α x) = (−1) e
(α1/2 dx)n
n −αx2
n −n/2 αx2 d e
= (−1) α e
dxn
α 1/4 2 /2
−1/2
Ψn (x) = (2 n!) n
e−αx Hn (α1/2 x)
π
n −αx2
1/2 n −n/2 αx2 d e
Hn (α x) = (−1) α e
dxn
(a) n = 0
α 1/4 2
Ψ0 (x) = (20 0!)−1/2 e−αx /2 H0 (α1/2 x)
π
α 1/4 2
= e−αx /2 H0 (α1/2 x)
π
0 −αx2
0 −0/2 αx2 d e 2 2
1/2
H0 (α x) = (−1) α e 0
= eαx e−αx = 1
dx
α 1/4 2
α 1/4 2
Ψ0 (x) = e−αx /2 .1 = e−αx /2
π π
(a) n = 1
α 1/4 2 /2
Ψ1 (x) = (21 1!)−1/2 e−αx H1 (α1/2 x)
π
1 −αx2
−1/2 αx2 d e 2 2
H1 (α 1/2 1
x) = (−1) α e = −α−1/2 eαx e−αx (−2αx)
dx1
= 2α1/2 x
α 1/4 2
Ψ1 (x) = (2)−1/2 e−αx /2 2α1/2 x
π
3 1/4
4α 2
= xe−αx /2
π
Mathematics session I: Taylor series expansion
In Quantum mechanics, it is often required to express a
function f (x) around a point (x0 , coordinate). For chemists
the coordinate of interest is the point where the
wavefunction or potential energy surface are minimum.
Taylor series
d
f (x) = f (x) + f (x) (x − x0 ) +

x0 x0 dx x0
2
1 d
f (x) (x − x0 )2 +

2! dx 2 x0
1 d3
f (x) (x − x0 )3 ....

3! dx3 x0
n
1 d
f (x) (x − x0 )n

n! dx n x0
Fourier series
Not covered in this chapter as they involve integrations. I
chose to do this in second chapter.
Worked example
Expand sin(x) around x = 0
d
sin(x) = cos(x)
dx
d2

d d d
sin(x) = sin(x) = (cos(x)) = − sin(x)
dx2 dx dx dx
d3
2
d d d
sin(x) = sin(x) = (− sin(x)) = − cos(x)
dx3 dx dx 2 dx
d4 d5
sin(x) = sin(x); sin(x) = cos(x)
dx4 dx5
x=0
sin(x) −−→ 0 d3 x=0
3
sin(x) = − cos(x) −−→ −1
d x=0
dx
sin(x) = cos(x) −−→ 1 d4 x=0
dx sin(x) = sin(x) −−→ 0
dx 4
d2 x=0
sin(x) = − sin(x) −−→ 0 d5 x=0
dx2 sin(x) = cos(x) −−→ 1
dx 5
1
sin(x) = 0 + 1 × (x − 0) + × 0 × (x − 0)2 +
2!
1 3 1
× −1 × (x − 0) + × 0 × (x − 0)4
3! 4!
1 5 1
+ 1 (x − 0) ... + (−1)(n+1) (x − 0)(2n+1)
5! (2n + 1)!
1 3 1 5 1
sin(x) = x − x + x ... (−1)(n+1) x(2n+1)
3! 5! (2n + 1)!
1
Expand ex around x = 0; Expand 1+x
around x = 0
Mathematics session I: Maxima and Minima of a
function
The maxima or minima of a function f (x) can be found by
df (x) d2 f (x)
3 Calculate dx
and dx2
df (x)
3 Find the roots of the equation dx
=0
d2 f (x) d2 f (x)
3 Maximum if dx2
< 0; Minimum if dx2
> 0;
3 Substitute the roots of x into the function f (x) to

obtain the minimum or maximum
function
Calculate the maxima and minima of
2
sin(x)
d d
sin(x) = cos(x); sin(x) = − sin(x)
dx dx2
d π
sin(x) = 0 = cos(x); xn = nπ +
dx 2
d2
sin(x) = −1 for n = 0, 2, 4 .... ⇒ maximum

dx2 xn
d2
sin(x) = 1 for n = 1, 3, 5 .... ⇒ minimum

dx 2 xn
π 3π
f (x) = sin( ) = 1; f (x) = sin( ) = −1

xn 2 xn 2
function
f (x) = x3 − 3x2 − 24x − 1
function
f (x) = x3 − 3x2 − 24x − 1
df (x)
= 3x2 − 6x − 24 = 0 ⇒ x2 − 2x − 8 = 0
dx
⇒ x = 4, −2
2
d f (x)
= 6x − 6
dx2
d2 f (x)
= 18 > 0 ⇒ minimum
dx2 x=4

d2 f (x)
= −18 < 0 ⇒ maximum
dx2 x=−2

f (x) = −81

x=4
f (x) = 27

x=−2
function
Plot of f (x) against x. x allowed to varie from -10 to 10.

function
Plot of f (x) against x. x allowed to varied from -3 to 5, to

show the maximum and minimum clearly.
function
The Lennard-Jones potential for
the interaction between two
molecules separated by a distance
R is
A B
U (R) = 12 − 6
R R
where A and B are constants. The
equilibrium separation Re is that
value of R at which U (R) is
mimimum and the binding energy
is De = −U (Re ). Express (i) A and
B in terms of Re and De , (ii) U (R)
in terms of R, Re and De
function
dU
= 0 = −12ARe−13 + 6BRe−7
dR R=Re

6BRe6 − 12A = 0
BRe6 − 2A = 0 (2)
A B
U (Re ) = 12
− 6 = −De
Re Re
6 12
A − BRe = −De Re (3)
A = De Re12
B = 2De Re12 /Re6 = 2De Re6
Tutorial: Theoretical
x
problems
Use the expansion of e around x=0, show that the Plank’s
blackbody radiation energy density equation convert into
Rayleigh-Jeans formula
8πh ν 3 dν
ρν (T )dν =
c3 e khν
BT − 1
2 n
hν hν 1 hν 1 hν
e kB T
−1 = + ... +
kB T 2! kB T n! kB T
2
hν hν
≈ 10−20 ≈0
kB T kB T
8πh ν 3 dν 8πkB T 2
ρν (T )dν = 3 hν
= ν dν
c k T c3
B
Correspondence principle: Quantum particle/wave behave
as classical particle at large quantum numbers
Tutorial: Theoretical problems
Find the wavelength at which the blackbody radiation energy density is
maximum ?
8πhc 1
ρλ (T ) = 5 hc
λ e λkB T − 1
hc 1 xkB T
let x = ⇒ =
λkB T λ hc
5 5 5
8πkB T x
ρx (T ) = 4 4 x
h c e −1
Calculate the maximum and minimum of the function

ρx (T )
d d
d f (x) g(x) dx
f (x)− f (x) dx
g(x)
=
dx g(x) g(x)2
d
f (x) = x5 ⇒ f (x) = 5x4
dx
d
g(x) = ex − 1 ⇒ f (x) = ex
dy
d 8πkB T (ex − 1)5x4 − x5 ex
5 5
ρx (T ) = =0
dx h4 c4 (ex − 1)2
5x4 (ex − 1) − x5 ex = 0
ex − 1 x5
= 4
ex 5x
x x
1 − e = ⇒ e−x + = 1
−x
5 5
x
e−x + =1
5
Newton-Raphson method
f (xn )
xn+1 = xn +
f 0 (xn )
x = 0, 4.956
0
ρx (T ) = ⇒ Rejected

x=0 0
To see whether ρx (T ) is a maximum or minimum, we have

to do a second derivative.
5
d 8πkB T 5 (ex − 1)5x4 − x5 ex
ρx (T ) = =0
dx h4 c4 (ex − 1)2
d2 5
T5 d (ex − 1)5x4 − x5 ex
" #
8πkB
ρx (T ) =
dx2 h4 c4 dx (ex − 1)2
x 4 5 x
f (x) = (e − 1)5x − x e
d x 3 4 x 5 x 4 x
f = (e − 1)20x + 5x e −x e − 5x e
dx
x 2 d x x
g(x) = (e − 1) ⇒ g = 2(e − 1)e
dx
2 x 2 x
d (e − 1) ((e − 1)20x − x e ) − ((ex − 1)5x4 − x5 ex )(2(ex − 1)ex )
3 5 x
ρx (T ) =
dx2 (ex − 1)4
20x3 (ex − 1)3 − x5 ex (ex − 1)2 − 10x4 ex (ex − 1) + 2x5 e2x (ex − 1)
=
(ex − 1)4
3 x 2 5 x x
20x (e − 1) − x e (e − 1) − 10x4 ex + 2x5 e2x
=
(ex − 1)3
20x3 (ex − 1)2 + x5 e2x + x5 ex − 10x4 ex
=
(ex − 1)3
= −11680243 ⇒ Maximum
hc
x = = 4.956
λkB T
hc
λmax T =
4.956 kB
6.6026 × 10−34 J s × 3.0 × 108 m s-1
λmax T =
4.956 × 1.380 × 10−23 J S-1
= 2.89609 × 10-3 m K
Wiens Law
Tutorial: Numerical problems
Conversion between frequency (ν, s-1 ) and wavelength (λ, m)
c 1 Power Unit
ν = ; ν̄ =
λ λ 1012 tera (Tm)
c = 3.0 × 10 m s-1
8
109 giga (Gm)
E = nhν = P t; P is power 106 mega (Mm)
Typical microwave frequency is 103 kilo (Km)
2.0 × 104 MHz. Calculate λ and 10-1 deci (dm)
E. 10-2 centi (cm)
ν = 2.0 × 104 MHz 10-3 milli (mm)
10-6 micro (µm)
= 2.0 × 104 × 106 s-1
10-9 nano (nm)
3.0 × 108 m s-1
λ = = 0.015 m 10-10 angstrom (Å)
2.0 × 1010 s-1
10-12 pico (pm)
E = hν = 6.6026 × 10−34 J s
10-15 femto (fm)
×2.0 × 101 0 s-1
10-18 atto (am)
= 1.32 × 10−23 J
1. Calculate the energy of a photon for a wavelength 100
pm ?
2. Calculate the number of photons in a 2.00 mJ light

pulse at (a)1.06 µm (b) 537 nm (c) 266 nm ?
3. What is the number of photons emitted per second by

a 1.0 mW nitrogen laser? The wavelength emitted by a
nitrogen laser is 337 nm.
Hint: Power (in units of W) is the energy per second
Calculating the surface temperature (T) of a blackbody
using Wien‘s law
λmax T = 2.89609 × 10-3 m K

The blackbody radiation energy distribution for Sun show
that maximum occurs at 500 nm wavelength. Calculate the
surface temperature of Sun?
2.89609 × 10-3 m K
T =
500 × 10−9 m
= 5792 K
1. At what wavelength does the maximum in the radiant

energy density distribution function for a blackbody
occur if (a)300 K (b) 3000 K (c) 10000 K ?
2. Sirius, one of the hottest known stars, has

approximately a blackbody spectrum with λmax =260
nm. Calculate the surface temperature of Sirius?
Calculating the threshold frequency (ν0 ) of a metal and
kinetic energy of ejected electrons in a photoelectron
spectroscopic measurements
hν = W + K.E
1
hν = hν0 + mv 2
2
1 eV = 1.602 × 10−19 J
The threshold wavelength for potassium metal is 564 nm.
What is its work function? What is the kinetic energy of
electrons ejected if radiation of wavelength 410 nm is used?
hc
W = = 3.512 × 10−19 J
λ0
hc
K.E = − W = 1.319 × 10−19 J
λ
1. Given that the work function of chromium is 4.40 eV,

calculate the kinetic energy of electrons emitted when
chromium surface is irradiated with ultraviolet
radiation of wavelength 200 nm?
2. When surface of silver irradiated with light of

wavelength 230 nm, the kinetic energy of the ejected
electrons is found to be 0.805 eV. Calculate the work
function and the threshold frequency of silver?
Tutorial: Hydrogen spectrum
Using the fundamental values for electron, calculate the value of Rydberg
constant and compare with the value deduced from experiment 109677.6 cm-1
me4
R∞ =
820 ch3
m = 9.10939 × 10−31 kg
e = 1.60217 × 10−19 C
0 = 8.85419 × 10−12 C2 N-1 m-1
c = 2.99792 × 108 m s-1
h = 6.626076 × 10−34 J s
kg C4
R∞ = 1.09737 × 107 2
C2 N-1 m-1 m s-1 (J s)3
kg
= 1.09737 × 107 -2 -1 3 2
N m J s
Tutorial: Hydrogen spectrum
Using the fundamental values for electron, calculate the value of Rydberg
constant and compare with the value deduced from experiment 109677.6 cm-1
d2 x
F = ma = m ⇒ N = kg m2 s-2
dt2
1 2
E = mv ⇒ J = kg m2 s-2
2
kg
R∞ = 1.09737 × 107 -2 -1 3 2
N m J s
kg
= 1.09737 × 107
kg m-4 s4 m-1 kg3 m6 s-6 s2
-2
-1
= 1.09737 × 107 m-1 = 1.09737 × 107 × 102 cm
= 1.09737 × 105 cm-1 = 109737 cm-1
109737 − 109677
error = × 100 = 0.055 %
109677
Calculating the wavelength corresponding to a line in the
atomic spectrum of Hydrogen using Rydberg equation.

1 1
ν̄ = 109677.6 − cm-1
n21 n22
n1 = 1 Lyman series
= 2 Balmer series
= 3, 4, 5 Paschen, Brackett, Pfund
Calculate the wavelengths of first three lines of Lyman
series?
First line in Lyman series n1 = 1, n2 = 2

1 1 1
ν̄ = = 109677.6 − cm-1
λ 1 4
λ = 121.56 × 10−7 cm = 121.56 nm
1. A line in the Lyman series has a wavelength of

1.03 × 10-7 m. Find the original energy level of the
electron?
2. Show that Lyman series occurs between 91.2 nm and

121.6 nm. Similarly show that Paschen series occur
between 820.6 nm and 1876 nm
Calculate the ionization energy of Hydrogen?
Ionization is the process to remove the outer most valence
electron from its orbit and taking it away from the atom.
For Hydrogen stable ground state is n1 = 1. Ionization
means taking the electron to continuum (n2 = ∞).

1 1
ν̄ = 109677.6 − cm-1
n21 n22

1 1
= 109677.6 − cm-1
1 ∞
= 109677.6 cm-1
= 13.588 eV
Calculate the de Broglie wavelength for
(a) an electron with kinetic energy of 100 eV?
h
λ =
mv
1 2 1 m2 v 2 (mv)2
K.E = mv = =
2 2 m 2m
p h
mv = (2mK.E) ⇒ λ = p
(2mK.E)
K.E = 100 eV = 100 × 1.602 × 10−19 J
m = 9.1 × 10−31 Kg
λ = 0.122 nm
(b) an proton with kinetic energy of 100 eV?

Heisenberg uncertainty principle
∆x∆p ≥ h
Calculate the uncertainty in the position of the cricket ball
in the previous example if the uncertainty in speed
measurement by the laser gun is 3%?
v = 153 km hour-1 = 42.5 m s-1

3 3
∆v = v × = 42.5 m s-1 ×
100 100
= 1.275 m s-1
∆p = m∆v = 150 × 10−3 kg × 1.275 m s-1
= 0.19125 kg m s-1
h 6.625 × 10−34 kg m2 s-1
∆x ≥ ≈
∆p 0.19125 kg m s-1
≥ 34.64 × 10−34 m
Heisenberg uncertainty principle
What is the uncertainty in momentum and velocity if we wish to locate an
electron with in an atom, say, so that ∆x is approximately 50 pm?
m = 9.109 × 10−31 kg
∆x = 50 pm = 50 × 10−12 m
6.625 × 10−34 kg m2 s-1
∆p ≥
50 × 10−12 m
≥ 1.3 × 10−23 kg m s-1
1.3 × 10−23 kg m s-1
∆p = m∆v ⇒ ∆v = −31
= 1.4 × 107 m s-1
9.109 × 10 kg

CURAJ Quantum Chemistry An Introduction

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CURAJ Quantum Chemistry An Introduction

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Quantum chemistry

Chapter 1: Physical chemistry by D. A. Mcquarrie

Chapter 1: Quantum chemistry by I. N. Levine

Chapter 4: The chemistry maths book by Steiner

Stanislao reconsidered Avogadro law after 50

Reproduced from https://corrosion-doctors.org/Periodic/Periodic-Mendeleev.htm

Iron Black body radiation

I The Kinetic energy of electrons does not depend on

Electronic spectrum of Quantization

Wave particle duality

3 Electron revolve around a stationary state

The arguments of a trigonometric, exponential, logarithmic

Taken from Atkins physical chemistry

Taken from Atkins physical chemistry

Chapter 4- Differentiation: The chemistry Maths book by

d d sin x cos x cos x − sin x(− sin x) 1

Differentiate y = 2x3 + 3ex − 21 ln x

3 Substitute the roots of x into the function f (x) to

Plot of f (x) against x. x allowed to varie from -10 to 10.

Plot of f (x) against x. x allowed to varied from -3 to 5, to

Calculate the maximum and minimum of the function

To see whether ρx (T ) is a maximum or minimum, we have

2. Calculate the number of photons in a 2.00 mJ light

3. What is the number of photons emitted per second by

λmax T = 2.89609 × 10-3 m K

1. At what wavelength does the maximum in the radiant

2. Sirius, one of the hottest known stars, has

1. Given that the work function of chromium is 4.40 eV,

2. When surface of silver irradiated with light of

1. A line in the Lyman series has a wavelength of

2. Show that Lyman series occurs between 91.2 nm and

(b) an proton with kinetic energy of 100 eV?

v = 153 km hour-1 = 42.5 m s-1

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