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)Thomson’s 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 (a particle) were deflected as they passed through a
Gold foil
» Conclusion: Heavy, tiny nucleus and much empty space in an atom
 Millikan’s Experiment

X-rays

X-rays give some drops a charge by knocking

off electrons
 Millikan’s Experiment

- -

+ +

They put an electric charge on the plates

 Millikan’s Experiment

- -

+ +

Some drops would hover

 Millikan’s Experiment
- - - - - - -

Some drops would hover

+ + + + + + +
 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  nh = integer > 2
E  RH  2  2 
 RH = Rydberg constant = 1.097 x 107 m-1
 2 nh 
B.Atomic Spectra
• Balmer described the emission spectrum of H in 1885
h = Planck’s constant = 6.626 x 10-34 J s
n = frequency of light s-1
–. hc c = speed of light = 2.998 x 108 m/s
E  hn   hcn
l l = wavelength nm
n = wavenumber cm-1

–.
 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 doesn’t 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

Absorption spectrum of
Gas

Emission spectra of
various elements
 Balmer’s 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
Bohr’s Model of the Hydrogen Atom
(1913)

He proposed that only certain orbits for the

electron are allowed
 Bohr’s 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

Bohr’s formula:
2)Bohr’s 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 Balmer’s equations with better ones
1 1 1
 1 1   
E  RH  2  2 
 m me mnucleus
 nl nh 
– Energy levels are far apart at small n, close together at large n
– Only worked for H-atom; not a complete description of atomic
structure
m = reduced mass
2 2 4
2p mZ e e = electron charge
RH  Z = nuclear charge
( 4pe o ) 2 h 2
4peo = permittivity of vacuum
Hydrogen is therefore a fussy
absorber / emitter of light

It only absorbs or emits photons with precisely the

right energies dictated by energy conservation
 Mechanics Wave Atomic Theory

ELECTROMAGNETIC RADIATION

• Subatomic particles (electron, photon, etc) have both

PARTICLE and WAVE properties
• Light is electromagnetic radiation - crossed electric and
magnetic waves:

Properties :
Wavelength, l (nm)
Frequency, n (s-1, Hz)
Amplitude, A
constant speed. c
3.00 x 108 m.s-1
 Electromagnetic Radiation

wavelength
Visible light

Amplitude

wavelength Node
Ultaviolet radiation
 Electromagnetic Radiation

• All waves have:

frequency and wavelength
• symbol: n (Greek letter “nu”) l (Greek “lambda”)
• units: “cycles per sec” = Hertz “distance” (nm)

• All radiation: l • n = c

where c = velocity of light = 3.00 x 108 m/sec

Note: Long wavelength

 small frequency
Short wavelength
 high frequency increasing increasing
frequency wavelength
 Quantization of Energy
Max Planck (1858-
(1858-1947)
Solved the “ultraviolet
catastrophe”
4-HOT_BAR.MOV

• Planck’s hypothesis: An object can only gain or lose

energy by absorbing or emitting radiant energy in
QUANTA.
 Quantization of Energy

Energy of radiation is proportional to frequency.

E = h•n
where h = Planck’s constant = 6.6262 x 10-34 J•s

Light with large l (small n) has a small E.

Light with a short l (large n) has a large E.

 Photoelectric Effect
Albert Einstein (1879-1955)

Photoelectric effect demonstrates the particle nature of light.

No e- observed until light

of a certain minimum E is used.

Number of e- ejected does NOT

depend on frequency, rather it
depends on light intensity.
 Application of the Schrödinger
Equation to the Hydrogen Atom
The potential energy of the electron-proton
system is electrostatic:

Use the three-dimensional time-independent

Schrödinger Equation.
• For Hydrogen-like atoms (He+ or Li++), replace
e2 with Ze2 (Z is the atomic number).
• In all cases, for better accuracy, replace m with
the reduced mass, m.
 Spherical Coordinates
•The potential (central force) V(r)
depends on the distance r
between the proton and
electron.

Transform to spherical polar

coordinates because of the radial
symmetry.
 The
Schrödinger
Equation in
Spherical
Coordinates
Transformed into spherical
coordinates, the
Schrödinger equation
becomes:
 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 +½ or -½
 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
• s-orbitals are spherical.
• There is one s-orbital per shell (n).
1s
•A total of 2 electrons per s orbital.
•No directionality.

2s

3s
 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 d-orbitals.
 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 orbitals.
 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 (-1…0…+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 “+½ or -½”
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 14e-

Electrons like to be in “pairs” !

1 1
 
2 2
 Fitting Quantum Numbers Together
Principal n=1 n=2 n=3
level (shell)

Sublevel
(subshell) s s p s p d
l=0 l=1 l=2

m=0 m=-1,0,1 m=-2,-1,0,1,2

Orbital s px py pz px py pz dxy dxz dyz dz2 dx2- y2

s= -½,+½
Spin
-½ +½
-½ +½ -½ +½ -½ +½ -½ +½ -½ +½ -½ +½ -½ +½ -½ +½ -½ +½ -½ +½ -½ +½

• n = # 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 1 2 3 4 ...n

l 0 0 1 0 1 2 0 1 2 3

Subshell
designation s s p s p d s p d f

Orbitals in
subshell 1 1 3 1 3 5 1 3 5 7

Subshell
capacity 2 2 6 2 6 10 2 6 10 14

Principal shell
capacity 2 8 18 32 ...2n2
 The Pauli Exclusion Principal

“No two electrons can have

the same four quantum
numbers.”
Aufbau Approach
Hund’s Rule
 Overlapping Orbitals

All orbitals overlap but electrons can’t be more

than 2 per orbital.
 “Had Enough??

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