Basic Atomic Theory and Atomic Orbitals: 2 Meet On Chemical Bond Course

Basic Atomic Theory
and Atomic orbitals

2st Meet on Chemical Bond Course
Atomic Structure
Basic Quantum Mechanics

Subatomic Particles
The Electron
J. J. Thomson credited with the discovery in 1897

Previously, atoms were believed to be the smallest particles
William Morgan (1785)passed current through a vacuum
Produced a glow
iii.Luigi Galvani (1800)first produced constant current from a
battery
Cu (wet salt solution) Sn Ecell = +0.48 V
iv.Michael Faraday (1836)determines glow comes from the
cathode
v. Eugene Goldstein (1876)coins the term cathode ray
vi.Thomson finds electron is negatively charged with 1/1836
mass of H
b)Thomsons Experiment
i) Repulsion from negative pole of an electric field meant

that the cathode rays must be negatively charged
ii)The amount of deflection was a function of the mass of
the ray
iii)Since many different metals all produced the same
cathode rays, all atoms must be made up of the
same +/- particles
iv)G. F. FitzGerald renames cathode rays as Electrons
2)The Nucleus
Ernest Rutherford credited with discovering the Nucleus
in 1911
He nuclei ( particle) were deflected as they passed
through a Gold foil
Conclusion: Heavy, tiny nucleus and much empty
space in an atom
3)The Proton
Rutherford and Moseley quickly discovered the charge of the nucleus
Electron beams aimed at an element caused X-rays to be emitted
The square root of the X-ray frequency emitted had a linear
relationship with about half of the atomic mass of the element
This number was clearly Z, the nuclear charge (or the atomic
number)
1
1
E RH 2 2
B.Atomic Spectra
2 nh
nh = integer > 2
RH = Rydberg constant = 1.097 x 107 m-1
Balmer described the emission spectrum of H in 1885

.
E.
hc
hc
h = Plancks constant = 6.626 x 10-34 J s

= frequency of light s-1
c = speed of light = 2.998 x 108 m/s
= wavelength nm
= wavenumber cm-1
n = principle quantum number = discrete allowed energies for H

electrons
Hydrogen Atom is Unstable?

It is known that accelerating charges emit
radiation
Thus, electron should emit radiation, lose energy
and eventually fall into the nucleus!
Why doesnt this happen? Shows that something
was wrong with this model of the hydrogen atom
Absorption Spectrum of a Gas
Dark lines will appear in the light spectrum
Absorption spectrum of
Sun
Emission spectra of
various elements
Balmers Formula for Hydrogen

Notice there are four bright lines in the hydrogen
emission spectrum
Balmer guessed the following formula for the
wavelength of these four lines:
where n = 3, 4, 5 and 6
Bohrs Model of the Hydrogen Atom

(1913)
He proposed that only certain orbits for the

electron are allowed
Bohrs Empirical Explanation

Electrons can only take discrete energies
(energy is related to radius of the orbit)
Electrons can jump between different orbits

due to the absorption or emission of photons
Dark lines in the absorption spectra are
due to photons being absorbed
Bright lines in the emission spectra are
due to photons being emitted
Absorption / Emission of
Photons
and Conservation of Energy
Ef - Ei = hf
Ei - Ef = hf
Energy Levels of Hydrogen
Electron jumping to
a higher energy level
E = 12.08 eV
Spectrum of Hydrogen
Bohrs formula:
2)Bohrs Quantum Theory of the Atom (1913)

Negative electrons move in stable, circular orbits around positive
nuclei
Electrons absorb or emit light by moving out or moving in to other
orbits
Bohr replaced Balmers equations with better ones
1
1
E RH 2 2
nh
nl
1
1
1
me mnucleus
= reduced mass
2 Z e
e = electron charge
RH
2 2
Z = nuclear charge
(4levels
Energy
o ) h are far apart at small n, close together at large n
4o = permittivity of vacuum
n = if the nucleus and electron are completely separate
2
2 4
Only worked for H-atom; not a complete description of atomic

structure
Hydrogen is therefore a fussy

absorber / emitter of light
It only absorbs or emits photons with precisely the

right energies dictated by energy conservation
Quantum Numbers and Orbitals

The equations predicted that there
are four quantum numbers.
Principal Quantum Number n (main energy level or
shell)
Angular Quantum Number l (orbital shape)
n l together is called a subshell
Magnetic Quantum Number m (orientation of
orbital)
Spin Quantum Number either + or -
Principal Quantum Number n

Designates the Main Energy Level or
Shell an Electron can Occupy
Orbital sizes increase as n increases.

n2 designates the maximum number of orbitals
allowed.
2n2 designates total electrons in an energy level
n= 1 has only 1 orbital; and 2 electrons

n=2 has 4 orbitals; and 8 electrons
n=3 has 9 orbitals; and 18 electrons
Angular Quantum Number l

Designates the shape of a sublevel
l= 0 through (n-1)
The sublevels are
s (sharp) where l=0
p (principal) where l=1
d (diffuse) where l=2
f (fundamental) where l=3
Another name for sublevel is orbital.
s (sharp) Sublevel
1s
2s
3s
s-orbitals are spherical.

There is one s-orbital per shell (n).
A total of 2 electrons per s orbital.
No directionality.
p (principal) Sublevel
Three of these
P orbitals are peanut shaped.

There are three p-orbitals per shell (n) and
have directionality along the x, y, and z-axis.
There are two electrons in each p-orbital.
A total of 6 electrons in all p-orbitals.
d (diffuse) Sublevel
Two of these
One of these
Two of these
d-orbitals are double peanut shaped.

There are five d-orbitals per energy level and
have complex directionality .
There are 2 electrons per d-orbital.
There are a total of 10 electrons in all dorbitals.
f (fundamental) Sublevel
One of these
Two of these
Two of these
Two of these
f orbitals are flower shaped.

There are seven orbitals and have
directionality
There are 2 electrons per f-orbital.
There are a total of 14 electrons in all 7
Angular Quantum Number m

Designates the orbitals in the subshell
Orbitals are oriented on a 3-dimensional axis.
m= -l to +l
For :
l=0 (s); m=0 (-0 to +0)
l=1 (p); m=3 (-10+1)
l=2 (d); m=5 (-2..-1..0..+1..+2)
l=3 (f); m=7 (-3..-2..-1..0..+1..+2..+3)
There are always 2

electrons per orbital!
What is a subshell?
A subshell is the principal quantum
number n together with the angular
quantum number l.
The n=1 shell has only one subshell which is the 1s subshell.
The n=2 shell has two subshells which are the 2s and 2p subshells.
There are a total of 4 orbitals in these subshells. One in the 2s and
three in the 2p.
Then=3 shell has three subshells which are the 3s, 3p and 3d. There
Are a total of 9 orbitals in these subshells, one in the 3s, three in the
3p and 5 in the 3d.
Try n=4 for yourself..
Spin Quantum Number + or -

Designates the spin of each electron in an
orbital
Each orbital can hold only 2 electrons.
s has 2e-; p has 6e-; d has 10e-; f has 14eElectrons like to be in pairs !
Fitting Quantum Numbers Together

Principal
level (shell)
n=1
Sublevel
(subshell)
l=0
n=3
l=1
m=-1,0,1
m=0
s
Orbital
n=2
px
py
pz
l=2
m=-2,-1,0,1,2
px
py
pz
dxy
dxz
dyz
dz 2
d x2 - y 2
s= -,+
Spin
- +
- + - +- + - + - +- +
- +
- +
- +
- +
- +
= # of sublevels per principal energy level
n2 = # of orbitals per principal energy level

2n2 = # of electrons per principal energy level
Quantum Number Relationships in

the Atomic Structure
n
2
0
3
1
Subshell
designation
Orbitals in
subshell
Subshell
capacity
Principal shell
capacity
18
10
10 14
32
...2n 2
The Pauli Exclusion Principal
No two electrons can have

the same four quantum
numbers.
Overlapping Orbitals
All orbitals overlap but electrons

cant be more than 2 per orbital.
Had Enough??
Read
Section 42!
Chem
istry
"Teacher, may I be excused? My brain is full."

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Basic Atomic Theory

and Atomic orbitals

Basic Quantum Mechanics

J. J. Thomson credited with the discovery in 1897

i) Repulsion from negative pole of an electric field meant

Balmer described the emission spectrum of H in 1885

h = Plancks constant = 6.626 x 10-34 J s

n = principle quantum number = discrete allowed energies for H

Hydrogen Atom is Unstable?

Absorption Spectrum of a Gas

Dark lines will appear in the light spectrum

Balmers Formula for Hydrogen

Bohrs Model of the Hydrogen Atom

He proposed that only certain orbits for the

Bohrs Empirical Explanation

Electrons can jump between different orbits

Energy Levels of Hydrogen

2)Bohrs Quantum Theory of the Atom (1913)

Only worked for H-atom; not a complete description of atomic

Hydrogen is therefore a fussy

It only absorbs or emits photons with precisely the

Quantum Numbers and Orbitals

Principal Quantum Number n

Orbital sizes increase as n increases.

n= 1 has only 1 orbital; and 2 electrons

Angular Quantum Number l

Another name for sublevel is orbital.

s-orbitals are spherical.

P orbitals are peanut shaped.

d-orbitals are double peanut shaped.

f orbitals are flower shaped.

Angular Quantum Number m

There are always 2

Spin Quantum Number + or -

Fitting Quantum Numbers Together

= # of sublevels per principal energy level

n2 = # of orbitals per principal energy level

Quantum Number Relationships in

The Pauli Exclusion Principal

No two electrons can have

All orbitals overlap but electrons

"Teacher, may I be excused? My brain is full."

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