General Chemistry (CHEM F111)

Lecture 10
11-11-2022

1
 RECAP
Principal quantum number, n: Energy Levels
1 1 
E = hcRH  2 − 2  h = E Accurate Ionization energy can
1   be determined

Hydrogenic spectra
Energy hcRZ2
En = -
n2
Orbital Angular Momentum J = [l(l+1)]ħ
Z-component of Angular Momentum Jz= ml ħ
Rnl(r)  r l. (Polynomial of degree n-l-1). e-Zr/na0
▪ The first-factor r l determines the behavior at r = 0 (only l = 0 wavefunctions are
nonzero at the origin)
• the second factor Polynomial of degree n-l-1 determines the number of radial
nodes (n-l-1)
• e-Zr/na0 ensures that the function goes to 0 as r →  Rnl(r)  r l e-Zr/na0
 RECAP
➢In general, the number of orbitals in a shell of principle
quantum number n is n2. ℓ sublevel
0 s
❖Shape of orbital sublevels ℓ = 0,1,2,..n-1
1 p
2 d
Magnitudes of Angular momentum 3 f
4 g
Magnetic Quantum Number, ml
❖Orientation of the orbital in space. Values of ml : integers -l to l
Z-component of angular momentum is quantized
Orbitals: The electron is much more likely to be found in certain
regions of atom than in others.
➢A 2s orbital is spherical, so its boundary surface is a sphere
 Zr 
Radial node is at  2s   2 - Zr e − Zr / 2 a0 


2 -
a

=0
0 
 a0  2a 0
r =
Z
For ns orbital: number of radial nodes = n -l- 1. Since l = 0 for s orbital, hence the no. of radial
3
nodes for ns is n-1
Different radial functions

Radial nodes
Angular part of the wavefunctions
 3s ORBITAL (n=3, l=0 and ml=0)

 4Zr 4Z 2 r 2  − Zr / 3a0
 3s   6 - + 2
e

 a0 9a 0 
Quadratic equation will have two solutions, so there
will be 2 radial nodes, 2 nodal surfaces

Total Number of Nodes : n-1

Number of radial nodes = n - l - 1
Number of angular nodes = l
A region in which the probability of finding an
electron is zero.

1s 2s 3s
 Number of radial
nodes = (n - l – 1)
Number of
angular nodes = l
 Wavefunction ; 2pz orbital

1 1 1
 3 2
1 1  2
r − r 2 a0  1 2 −r
 2 Pz =   cos  3  e 
= 5
 r cose 2 a0

 4  2  6a0  a0  32a0 

angular
radial
component
component

When is this function going to be zero?

❖θ=π/2 xy plane is a nodal plane
 2P Orbitals No. of nodes = n-1 =1

• Each p subshell consists of 3 orbitals (ml = +1, 0,-1)

• l = 1 , There is only one angular node
•There are no radial nodes

Angular node is a nodal plane

 p orbitals – angular parts

α cos  (pz) α sin  sin  (py) α sin  cos  (px)

l = 1, ml = 0 l = 1, ml = 1 or –1 l = 1, ml = 1 or –1
1 nodal surface(xy) 1 nodal surface (xz) 1 nodal surface (yz)

Note that in spherical polar coordinate: x= r sin cos;

y = r sin sin; z = r cos
 3d orbitals
Each d subshell consists of 5 orbitals (ml = +2,+1, 0,-1, -2)
❖ There are no radial nodes
2 angular nodes (nodal
planes) (l = 2)

nodal planes perpendicular to

each other except for dz2

dz2 - nodes
are conical surfaces with
apexes at the nucleus
Normalized Hydrogen-like wave functions
Use of wavefunction – Description of H atom

Probability of finding the electron at

a distance between r+dr from
nucleus, with its angular coordinates
d
having values between +d and
+ d (an infinitesimal volume
element d) is
ψn,l,ml(r,,)  ψ
ψ ψ* d = [Rn,l(r)]2 [Yl,ml(,)]2 r2 dr sin dd

Volume element d = r2 dr sin dd

 Use of wave functions – Description of H atom

ψ ψ* d = [Rn,l(r)]2 [Yl,ml(,)]2r2 dr sin d d

To determine the Probability that electron between the
distance r+dr from nucleus, regardless of angle ( and )
can be obtained by integrating over  and 

Integral of [Yl,ml(,)]2 can be normalized to

unity (1)
 2
[Yl,ml(,)]

2 sin d d =1

0 0
Radial distribution for s - electrons
Tells us the probability of finding an
electron at a distance from the nucleus
regardless of the direction
Consider two spherical shells centered on the nucleus one
of radius r and other of radius r +dr.

The probability of finding an electron inside a small volume

of magnitude δV is = ψ2δV
Volume = Surface area of the inner shell  4πr2dr
thickness of the region

Probability = ψ2δV = P(r)dr = 4πr2 ψ2 dr

 Radial distribution
ψ ψ* d = [Rn,l(r)]2 [Yl,ml(,)]2r2 dr sin dd

Integral of [Yl,ml(,)]2 is normalized to unity (1)

 2
Or, 
[Yl,ml(,)]2 sin dd =1
0 0
Radial Probability, P(r)dr
P(r)dr = [Rn,l(r)]2 r2 dr
Radial probability distribution P(r) =r2[Rn,l(r)]2
function
Radial probability :
General expression, P(r)dr = [Rn,l(r)]2 r2 dr
for orbitals that depend on angles
Radial distribution for s - electrons
Probability = P(r)dr = 4πr2dr
4πr2 ψ2 dr
Radial distribution FUNCTION P(r)= 4πr2 ψ2

The electron will be found with the same probability in

any direction for S- electrons
 Radial Probability for s electrons = 4πr2 ψ2δr
The factor 4πr2 arises because the radial distribution
function refers to the probability of finding an electron
not at a specific point in space but on a spherical shell of
area 4πr2, at a distance r from the nucleus
 P(r) = 4πr2ψ1s2

The most probable radius

is the ground state radius
obtained from the Bohr
theory.
The Schrödinger equation
confirms the first Bohr
radius as the most probable
radius and also goes further
4 0  2 to describe in detail the
Bohr radius a0 = m e 2 profile of probability.
e
Use of wavefunctions – Most probable radius

Probability, P(r)dr=(4r2ψ2)dr
P(r)dr = [Rn,l(r)]2 r2 dr

Most probable radius can be calculated from

probability distribution, dP(r)/dr=0

For lowest state, n=1, l=0

Most probable radius = a0

 electron density

wave function

radial probability
distribution
1s

2s
 Probability distribution in H
Radial probability of finding electron is always
small near nucleus as r2 factor is small
 Hydrogenic Atom Wavefunctions
•Position of principal (largest) maximum depends
on n and l
•For fixed n it moves to shorter r values as l
increases(r2p)max < (r2s)max ;

(r3d)max < (r3p)max< (r3s)max

 H- atom spectra
Does l, m have any role in
determining spectra? Or only n
determines that?
 Are all transitions possible?

• We have seen that each

state with quantum 32
number n have total n2
subshells (or, n2 fold
degenerate 22

• Are transitions between all

possible values of l and m 12
are possible?
 Spectral Transitions- Selection Rules
Not all transitions between all available states are
possible

2p to 1s, and 3p to 1s are allowed transitions

2s to 1s or 3d to 1s are forbidden transitions.
Selection rule.
A statement that says which spectroscopic
transitions are allowed and which are forbidden
 Selection rule:
• Photons have intrinsic angular momentum
• Law of conservation of angular momentum
implies that when a photon is emitted or
absorbed by an atom then angular momentum
quantum number must change by unity

Selection rule: Allowed transitions: contribute

l = ± 1 to spectrum
ml = 0, ± 1 s→p; p→ s; p→d; d→p;
d→f…….

Forbidden transitions: can not contribute to spectrum

d (l=2)→s (l=0); s (l=0)→s (l=0);
 Grotrian diagram

The selection rules

and the atomic
energy
levels jointly
account
for its structure
 Selection rule:
Allowed transitions: contribute to spectrum
s→p; p→ s; p→d; d→p; d→f……. Are allowed!
Forbidden transitions: can not contribute to
spectrum
d (l=2)→s (l=0); photon cannot carry this much
angular momentum
s (l=0)→s (l=0); photon fails to transfer its angular
momentum as it remains unchanged for electron
are forbidden!