The Quantum Nature of the Atom Silberberg: Ch.

7-8
Hydrogen: makes the world around
us, simplest atom in the world Structure can be studied by looking at the interaction between electromagnetic
radiation and matter.
Where we're going: The nature of light
Why do we care about e? electrons can move around, be Wave-particle duality
transfered or shared through ionic and covalent bonds in a rxn
The quantum nature of the atom:
the Schrödinger model of the Hydrogen atom
Why did we start with light? because a lot of rxns happen
when light is present and there is an important relationship - atomic orbitals
between electromagnetic radiation and electrons
- quantum numbers
- quantized energies
electromagnetic radiation: a wave of energy that travels
through space (light wave has electricmagnetic radiation) - how do we know that the
sub-microscopic world is quantized?

From one-electron atoms to

many-electron atoms: what's different?
Electron configuration and periodicity
- originally, a form of energy thought of as waves traveling through space
this figure shows the relationship
between wavelength and frequency
- travels (in a vacuum) at the speed of light (c = 3.00 x 108 m/s)

Wave characteristics:

1. wavelength (λ, lambda):

Amplitude
distance between 2 peaks or 2 troughs t
unit: m
Although the unit is m, wavelength is usually calculated in nm
1m=10^9 nm
2. frequency (ν, nu): number of waves per second that passes through a
given point (how often the wave hits the same point).
units: s^-1, Hz (Always keep track of your units!)

Amplitude
t
νλ=c
1/s m 3.00x10^8 m/s
 How does microwave work? makes the water molecule excited and
produces kinetic energy which makes the food become warmer!

The field of
nuclear energy

Sun

Important: The longer the wavelength, the lower the frequency (wavelength and frequency are proportional)

νλ=c
 3. amplitude (A): height of wave
- an interference
of waves:
Amplitude diffraction

the double slit

experiment

When waves interact, amplitude can change, ampliture is classicaly related to the energy of light

waves interfere: constructive destructive

If the peaks and troughs add up -> constructive
“ “ “ “ “ “ “ “ “ “ “ “ don’t add up -> destructive
3. amplitude (A): classically related to energy (intensity) of light

- light of greater amplitude appears brighter

Light – has many wave properties but does not
behave as classical wave The photoelectric effect:
photons=come in packets particles of energy
Current: the flow of e
Energy of light is more related to frequency than intensity
More intensity=more electrons, but not more kinetic energy

1. To eject an electron from the metal, E photon= binding+ KE

a minimum frequency of light is necessary. E photon=hv
energy =hc/λ
interaction between metal surface= binding energy e- with
2. Above this minimum frequency, the kinetic energy Plank’s constant: kinetic energy
a photon is nothing more than an energy h=6.626 x10^-34 Js
of the ejected electron increases with light frequency. light
The total energy in=the total energy out
we have enough energy to get the electron come off
3. Above this minimum frequency, increased light intensity increases
energy -> # of photons
the number of ejected electrons but not their kinetic energy. metal
The more photons=the more energy we can get
A green laser pointer emits lights having a wavelength of 532 nm. A red laser pointer emits light having a
wavelength of 656 nm.

1. Which light has a greater frequency? Green or Red The greater frequency=greater energy
Green, the smaller the wavelenght= the greater the frequency “ “ wavelenght= smaller (less) energy

2. Which light has a greater energy? Green or Red

Green, the greater the frequency, the greater the energy
The greater the wavelenght, the smaller the energy

3. A laser pointer emits 4.0 mW of light at 532 nm. How many photons of light are emitted in one minute?
(1.00 W is 1.00 J/s)
Answered it on the notebook!
Warm Up Questions
Of the two waves shown below, which most accurately depicts electromagnetic
radiation of higher energy?

Wave A

Wave B
Originally, matter: - discrete particles with determinate mass, position, etc. beam of electrons

The double-slit experiment revisited:

particles behave different than waves, electron diffract (wave property, not particles property)

particles waves electrons

? ?
?
?
?
? ?
? ?
?
? ?
? ?
?

the waves diffract each other (the

Where the waves interfere, the way that particles pass through is
middle of the waves is the maximum basically different than waves)

Either the balls (particles)

pass through here, or bounce waves bend out like circles
electrons diffract!

most waves, constructive

destructive interference
interference waves
(where the troughs are)
Passage of electricity through gas of atoms causes atoms to emit light

The diffraction of electrons is a wave

property and not electron property.

Glowing!

H-atoms
Passage of electricity through gas of atoms causes atoms to emit light
Visible frequencies
410 nm
ACTUALLY observed only four frequencies
434 nm 656 nm
in visible part of spectrum: 486 nm

H2 molecules: 2H
Hydrogen atoms glow (emits light)
The narrow light is detecting screen
H-atoms Prism-> separates the wavelength or frequency
These observed frequencies are
different for excited atoms of
different elements.
The frequency observed are different for excited atoms of
different elements -> because there are different energy levels
 Before 1900:
light: wave character – e.g. wavelength, frequency, diffraction
matter: particulate character – e.g. mass, position

photoelectric effect

experiments
diffraction by electrons
atomic line spectra

Wave-particle duality:
light: Both wave and particular charachter
matter:
 Matter has wave characteristics as well as particle characteristics

Schrödinger model of the atom:

HY = EY wave equation
t of ical Symbol psy
t
se ma ns
e tio solve
a h
t ra
m pe Y = "wavefunction" or "orbital"
o
- has many solutions Y = a mathematical function
Has many solutions -> a mathematical describing the shape of a wave
function describing the shape of wave

Ψ^2= probability of finding

electron at any point in nucleus
 HY = EY wave equation – has many solutions Y

Y = "wavefunction" or "orbital"
orbitals: max 2 electrons must be spinning up and down

1. principal quantum number (n)

® Tells us the distance between
nucleus and electron, size
2. angular momentum quantum number ( ! )
Each orbital is described by 3quantum #
® Shape of the orbital
Quantum: some sets of values
3. magnetic quantum number (m! or m)
® Orientation of the orbital
4. electron spin quantum number (ms or s)
ms = can think of e as a spinning
charge of particles

ms=-1/2 ms=+1/2
 Size of the orbital Shape of the orbital

1. principal quantum number (n) 2. angular momentum quantum number ( ! )

n = 1, 2, 3, ... ! = 0, 1, … , n-1

The hydrogen atom is predicted to have:

Orientation of the orbital an s orbital for n = 1;
3. magnetic quantum number (m! or m) s and p orbitals for n = 2;
m = -!, -!+1, … , !-1, ! s, p, and d orbitals for n = 3;
Angular momentum depends on the quantum #
Magnetic quantum #depends on angular momentum and so on…
L: 0 S quantum #: tells the size S orbital -> n=1
# +letter S and P orbitals -> n=2
n ! Notation m! Number of orbitals S1P1 and d orbital -> n=3
and so on
L:1 P 1 0 1S 0 1
2 0 2S 0 1
2 1 2P -1,0,1 3
L:2 d 3 0 3S 0 1
3 1 3P -1,0,1 3
3 2 3d -2,-1,0,1,2 5
Among these five sets of quantum numbers:
I. n = 3, l = 2, ml = -2
II. n = 3, l = 1, ml = 0
III. n = 3, l = 0, ml = -1
IV. n = 3, l = 2, ml = 0
V. n = 3, l = 3, ml = -2
which does not describe a state for an electron in
an atom?
A. II and IV
B. III and V
C. I and III
D. IV and V

3 2 3d -2, -1, 0, +1, +2

 Warm Up Question

How many orbitals are there in the subshell designated by n = 3, l = 2?

A. 2 n=3 principle size

l= angular momentum shape
B. 3 m l= orientations
C. 5 notation: 3d
D. 6
E. 10
Solving H Y = E Y for H-atom,

1s orbital: n = 1, ! = 0, m! = 0 2s orbital:
higher probability of finding electrons close to nuclus n = 2, ! = 0, m! = 0
why does it go to 0? because of Schrödinger's equation
As you increase the n, you increase the size and the # of nodes

"wave-like"!
radial probability: sum of all
probable electrons that have
the same distance to nucleus
as there is no particular point
that has the same distance

As n increases, the
at 4, there is a low
probability to find size of the orbital
electron and number of
at 1.3 -> node: zero probability nodes increase.
This picture is misleading, there is no bondry in finding electrons of finding an electron
 2p orbitals: 3d orbitals:
The lowest quantum # where we have p orbital is 2
m l=n-1,0,1 Orientation: 3 d orbitals: n=3, l=2
m l= -2, -1, 0, 1, 2

made up of 2 lobes
separaded by nodes

theres is a significant probability of finding electrons than

There are five 3d orbitals. Each has two nodes
the S orbital (indicating that the P orbital is basically bigger)
There are three 2P orbitals directed along
the x,y, and z axes. Each one has one node
From H Y = E Y, Schrödinger's equation: Electrons having wave properties, quantum numbers which have orbitals, we also get energy

many solutions
−0.242 x 10−18 J
subshell
Y = orbital subshell subshell
−0.545 x 10−18 J
E = energy of
each orbital excited state: anywhere that is not a ground state
Same n value= shell (Shells
For H-atom, This equation is only true for the H atome basically have the same n value)
The formula gives the energy where the electrons are in that particular order
1
* En = -2.18x10- 18 Jæç 2 ö÷ n is the principle quantum #
constant energy è n øthe energy orbital depends only
of the principle quantum # For every orbital,
- doesn’t depend on !, m ground state
Y describes relative
As long as the electron is
® subshells have the same energy −2.18 x 10−18 J not in the groundstate, it
shell probability of finding
is in excited state
(i.e. they are degenerate) The more negative the number, electron around nucleus
the lowe energy, the more stable
Energy of the atom is quantized! E tells us how stable it is
having that probability
Passage of electricity through gas of atoms causes atoms to emit light

ACTUALLY observed only four frequencies 410 nm

434 nm 656 nm
in visible part of spectrum: 486 nm

H-atoms
These observed frequencies are
different for excited atoms of
different elements.
 n
Historically more important bc they are in the visible range
∞
For the H-atom: 6 Infrared
In 1S orbital, there is higher probability 5
4 (>656 nm)
to find electrons closer orbitals
656 nm
−0.242 x 10−18 J 3
energy only depends on 486 nm Visible
434 nm
principle quantum # 410 nm
−0.545 x 10−18 J 2 H-atoms
more stable= lower energy
lower stable= greater energy Ultraviolet
2.18 ´10 -18 J (<400 nm)
En = -
n2 Detecting screen
This formula is for hydrogen atom only bc
hydrogen is the only atom that has 1 electron En It’s negative because the orbital goes toward the nucleus
We cannot store energy (photon), it either Final state: n = 2 E2= -5.45x10^-19 J
absorbs it or not (stays in its position)
Discrete emission lines Initial state: n = 3 E 3= -2.41 x10^-19 J
can only be explained △E=-3.02x10^-19 J The negative means that
we’re losing the energy
by quantization of the
energy levels of atoms We can’t have a negative photon, so
E photon=3.03x10^-19 J= hc/λ we just have it in the positive way
and molecules. λ = hc/3.03x10^-19 J
You have to give the gap, so the =656 nm (same as what we detected!)
electrons can excite the enrgy energy: inverly proportional to the wavelength
Historically less important
bc they are ultraviolent
−2.18 x 10−18 J 1
Absorptions Emissions because the photon is coming off, we call this an emission
The figure below represents the emission spectrum of a one-electron ion in the gas phase. All the
lines shown result from electronic transitions from excited states to the n = 3 state.

A B

Wavelength

A) A: n = 3 → n = 1; B: n = 2 → n = 1

B) A: n = 1 → n = 3; B: n = 1 → n = 2
What transitions correspond to A and B?
C) A: n = 6 → n = 3; B: n = 5 → n = 3

D) A: n = 5 → n = 3 ; B: n = 6 → n = 3

E) A: n = 3 → n = 1; B: n = 2 → n = 1
1. no two electrons in an atom can have the same values
of all 4 quantum numbers: Pauli exclusion principle

1. principal q. n. (n) 3. magnetic q. n. (m!)

n = 1, 2, 3, ... m = −!, −!+1, … , !−1, !

2. angular momentum q. n. ( ! ) 4. electron spin q. n. (ms)

! = 0, 1, … , n−1 ms = +1/2, −1/2

If, for an electron, n = 2, ! = 1, m = 0, ms = −1/2

Then, for any other electron, n = 2, ! = 1, m = 0, ms = −1/2

↓ N ↑

2. repulsions between the electrons within the atom

Effective nuclear charge, Zeff : the nuclear charge actually felt by an electron
Two factors determine an atom's energy:

1. electron-nucleus attractions; 2. electron-electron repulsions E.g. comparing a 2s electron to

a 2p electron:
electrons further from
nucleus are shielded many-electron atom: E2s < E2p

1s electron cloud
from full +ve nuclear
charge by electrons
closer to the nucleus

2s experience higher Zeff than 2p

Generally, for any given value of n: Ens < Enp < End < Enf
Outcome: for a many-electron atom, subshells are not degenerate: Ens < Enp < End < Enf

H-atom many-electron
atom
For (almost) all elements of the periodic table, we can now predict which orbitals are occupied by electrons
= the ground state (i.e. most stable) electron configuration:
1. Electrons will fill orbitals of lowest energy ('Aufbau')
2. 2 electrons per orbital with opposing spin (­ & ¯)
3. If two or more degenerate orbitals are available, one electron goes
into each until they are all half-full. All electrons in half-filled
orbitals have the same spin quantum number.

'Hund's rule' Order of orbital 6s 6p 6d …

filling with electrons:
5s 5p 5d 5f 5g
many-electron
4s 4p 4d 4f
atom
3s 3p 3d
2s 2p
1s
E.g. ground state electron configuration of P atom (Z = 15):

Ne
P

Note: some atoms do not follow these simple

rules. For our purposes, we will not consider
these anomalous electron configurations.
Structure of the atom from Schrödinger is evident in the structure of the periodic table
 pm pm
atomic size decreases

atomic size decreases

1. The 1s22s22px2 state of a carbon atom is
A. a ground state
B. an excited state

2. The electronic configuration of element X is 1s22s22p63s23p3. The formula of

the most likely compound that X will form with Ca is
A. CaX2
B. Ca2X3
C. Ca2X
D. Ca3X2
Light has both wave and particle properties = photons. Each photon has energy E = hν

Matter has both wave and particle properties

HY = EY ® cannot pinpoint electron’s position but can describe a PROBABILITY of finding the
electron around an atom
Y = orbital; Y2 = probability of finding the electron in a region of space about the atom.
Orbitals are regions where the electron spends most of its time; each uniquely specified
by its set of three quantum numbers (+ one quantum number specifying electron spin)
Energy levels of atoms and molecules are quantized (i.e. discrete). Transition between
energy levels occurs with either absorption (↑ in energy) or emission (↓ in energy) of a
photon of radiation of the corresponding energy (and therefore wavelength/frequency).
The absorption/emission spectrum of each element and compound is unique.

Quantum mechanics gives us the electronic configuration of atoms which helps us understand
their properties.