Atomic Orbitals

The numbers and types of atomic orbitals

depend on the principal energy level.
Summary of Principal Energy Levels and Sublevels
Maximum
Principal Number of
Type of sublevel number of
energy level sublevels
electrons
n=1 1 1s (1 orbital) 2

n=2 2 2s (1 orbital), 2p (3 orbitals) 8

3s (1 orbital), 3p (3 orbitals),
n=3 3 18
3d (5 orbitals)
4s (1 orbital), 4p (3 orbitals),
n=4 4 32
4d (5 orbitals), 4f (7 orbitals)
 Quantum Numbers

Quantum numbers are required to describe the distribution of

electron density in an atom.

There are three quantum numbers necessary to describe an atomic

orbital.

The principal quantum number (n) – designates size

The angular moment quantum number (l) – describes shape

The magnetic quantum number (ml) – specifies orientation

Spin Quantum Number ( ms )
Quantum Numbers

The principal quantum number (n) designates the size of the

orbital.

Larger values of n correspond to larger orbitals.

The allowed values of n are integral numbers: 1, 2, 3 and so forth.

The value of n corresponds to the value of n in Bohr’s model of the

hydrogen atom.

A collection of orbitals with the same value of n is frequently

called a principle energy level or shell.
 1s orbital imagined as “onion”

Concentric spherical shells

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Shapes of s, p, and d-Orbitals

s orbital

p orbitals

d orbitals
Atomic Orbitals
 s, p, and d-orbitals

A B C
s orbitals: p orbitals: d orbitals:
Hold 2 electrons Each of 3 pairs of Each of 5 sets of
(outer orbitals of lobes holds 2 electrons lobes holds 2 electrons
Groups 1 and 2) = 6 electrons = 10 electrons
(outer orbitals of (found in elements
Groups 13 to 18) with atomic no. of 21
and higher)
Kelter, Carr, Scott, , Chemistry: A World of Choices 1999, page 82
 21s 22s 23s

r r r r r r
Distance from nucleus

(a) 1s (b) 2s (c) 3s

 Quantum Numbers
y y y

z z z

x x x

px pz py
 p-Orbitals

px pz py

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 335

 y y y y

z z z z

x x x x

s px pz py

2s 2p (x, y, z) carbon

Mark Wirtz, Edward Ehrat, David L. Cedeno*

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
Quantum Numbers

The angular moment quantum number (l) describes the shape of

the orbital.

The values of l are integers that depend on the value of the

principal quantum number

The allowed values of l range from 0 to n – 1.

Example: If n = 2, l can be 0 or 1.

l 0 1 2 3
Orbital designation s p d f

A collection of orbitals with the same value of n and l is referred to

as a subshell.
 Quantum Numbers
2. Angular Momentum Quantum # ( l )
– Energy sublevel
– Shape of the orbital

s p d
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 The azimuthal quantum number
Second quantum number l
is called the azimuthal quantum number

– Value of l describes the shape of the region of space

occupied by the electron

– Allowed values of l depend on the value of n and can

range from 0 to n – 1

– All wave functions that have the same value of both n

and l form a subshell

– Regions of space occupied by electrons in the same

subshell have the same shape but are
oriented differently in space

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.

 A Cross Section of an Atom
n0
Rings of Saturn p+

1s 2s 2p 3s 3p 3d

The first ionization energy level has only one sublevel (1s).
The second energy level has two sublevels (2s and 2p).
The third energy level has three sublevels (3s, 3p, and 3d).

Although the diagram suggests that electrons travel in circular orbits,

this is a simplification and is not actually the case.
Corwin, Introductory Chemistry 2005, page 124
 Quantum Numbers
• Orbitals combine to form a spherical shape.

2s
2px
2py 2pz

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 Quantum Numbers
Principal n=1 n=2 n=3
level

Sublevel s s p s p d

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

• n = # of sublevels per level

• n2 = # of orbitals per level
• Sublevel sets: 1 s, 3 p, 5 d, 7 f

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 Maximum Capacities of Subshells
and Principal Shells
1 2 3 4 .
0 0 1 0 1 2 0 1 2 3
Subshell
nation s s p s p d s p d f
Orbitals in
ell 1 1 3 1 3 5 1 3 5 7
Subshell
ity 2 2 6 2 6 10 2 6 10 14
Principal shell
2 8 18 32 ...2

Hill, Petrucci, General Chemistry An Integrated Approach1999, page 320

Quantum Numbers
The magnetic quantum number (ml) describes the orientation of
the orbital in space.
The values of ml are integers that depend on the value of the
angular moment quantum number:
– l,…0,…+l
 Quantum Numbers
3. Magnetic Quantum Number ( ml )
– Orientation of orbital
– Specifies the exact orbital within each sublevel

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 The magnetic quantum number
Third quantum is ml, the magnetic quantum number
– Value of ml describes the orientation of the region
in space occupied by the electrons with
respect to an applied magnetic field
– Allowed values of ml depend on the value of l
– ml can range from –l to l in integral steps
ml = l, -l + l, . . . 0 . . ., l – 1, l
– Each wave function with an allowed combination of
n, l, and ml values describes an
atomic orbital, a particular spatial
distribution for an electron
– For a given set of quantum numbers, each
principal shell contains a fixed number of
Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
 d-orbitals

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 336

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
Principal Energy Levels 1 and 2
Quantum Numbers

Quantum numbers designate shells, subshells, and orbitals.

Worked Example 3.8

What are the possible values for the magnetic quantum number (m l) when the
principal quantum number (n) is 3 and the angular quantum number (l) is 1?
Strategy Recall that the possible values of ml depend on the value of l, not on
the value of n.

Setup The possible values of ml are – l,…0,…+l.

Text Practice: 3.81 3.82

Quantum Numbers

The electron spin quantum number (ms ) is used to specify an

electron’s spin.

There are two possible directions of

spin.

Allowed values of ms are +½ and −½.

Quantum Numbers

A beam of atoms is split by a magnetic field.

Statistically, half of the electrons spin clockwise, the other half

spin counterclockwise.
 Electron Spin: The Fourth Quantum Number

• When an electrically charged object spins, it produces a magnetic

moment parallel to the axis of rotation and behaves like a magnet.

• A magnetic moment is called electron spin.

• An electron has two possible orientations in an external magnetic

field, which are described by a fourth quantum number ms.

• For any electron, ms can have only two possible values, designated
+ (up) and – (down), indicating that the two orientations are opposite
and the subscript s is for spin.

• An electron behaves like a magnet that has one of two possible

orientations, aligned either with the magnetic field or against it.

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
Quantum Numbers

To summarize quantum numbers:

principal (n) – size
angular (l) – shape Required to describe an atomic orbital
magnetic (ml) – orientation

principal (n = 2)

2px related to the magnetic

quantum number (ml )

angular momentum (l = 1)

electron spin (ms) direction of spin Required to describe an

electron in an atomic
orbital
 3.8 Atomic Orbitals

All s orbitals are spherical in shape but differ in size:

1s < 2s < 3s

principal quantum
number (n = 2)

2s
angular momentum
quantum number (l = 0)

ml = 0; only 1 orientation
possible
Atomic Orbitals

The p orbitals:

Three orientations:
l = 1 (as required for a p orbital)
ml = –1, 0, +1
 Atomic Orbitals

The d orbitals:

Five orientations:
l = 2 (as required for a d orbital)
ml = –2, –1, 0, +1, +2
• http://mw.concord.org/modeler/showcase/simulation.html?s=http://
mw2.concord.org/public/student/quantumchemistry/atomicorbitals.html
Energies of Orbitals

The energies of orbitals in the hydrogen atom depend only on the

principal quantum number.

3rd shell (n = 3) 3d subshell (n = 3; l = 2)

3p subshell (n = 3; l = 1) 3s subshell (n = 3; l = 0)

2nd shell (n = 2)2p subshell (n = 2; l = 1)

2s subshell
(n = 2; l = 0)
 Quantum Numbers
• Pauli Exclusion Principle Wolfgang Pauli

– No two electrons in an atom can have the same 4

quantum numbers.
– Each electron has a unique “address”:
1. Principal #  energy level
2. Ang. Mom. # 
sublevel (s,p,d,f)
3. Magnetic # 
4. Spin #  orbital
electron

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 Allowed Sets of Quantum Numbers for Electrons in Atoms
Level n 1 2 3
Sublevel l 0 0 1 0 1 2
Orbital ml 0 0 1 0 -1 0 1 0 -1 2 1 0 -1 -2
= +1/2
Spin ms
= -1/2
 The Heisenberg Uncertainty
Principle
• Whenever a measurement is made there is
always some uncertainty
• Quantum mechanics limits the accuracy of
certain measurements because of wave –
particle duality and the resulting interaction
between the target and the detecting
instrument
 Heisenberg realized that ...
• In the world of very small particles, one
cannot measure any property of a particle
without interacting with it in some way

• This introduces an unavoidable

uncertainty into the result

• One can never measure all the

properties exactly
Werner Heisenberg (1901-
1976)
Image in the Public Domain
 Measuring Position and
Momentum of an Electron
• Shine light on electron and detect
reflected light using a microscope
• Minimum uncertainty in position BEFORE
ELECTRON-PHOTON
is given by the wavelength of the light COLLISION

• So to determine the position

accurately, it is necessary to use
light with a short wavelength

inciden
t
photon
electro
n
 Measuring Position and
Momentum of an Electron
• By Planck’s law E = hc/λ, a photon with a
short wavelength has a large energy
AFTER
ELECTRON-PHOTON
• Thus, it would impart a large ‘kick’ to the COLLISION
electron
But to determine its
momentum accurately,
electron must only be given a small kick

• This means using light of long

scattere
d
photon
wavelength !
recoilin
g
electro
 Implications
• It is impossible to know both the position and
momentum exactly, i.e., Δx=0 and Δp=0

• These uncertainties are inherent in the

physical world and have nothing to do with
the skill of the observer

• Because h is so small, these uncertainties are

not observable in normal everyday situations
 Example of Baseball
• A pitcher throws a 0.1-kg baseball at 40
m/s

• So momentum is 0.1 x 40 = 4 kg m/s

• Suppose the momentum is measured to an

accuracy
of 1 percent , i.e.,

Δp = 0.01 p = 4 x 10-2 kg m/s

 Example of Baseball (cont’d)

• The uncertainty in position is

then

• No wonder one does not observe

the effects of the uncertainty
principle in everyday life!
 One might ask:
“If light can behave like a particle,
might particles act like waves”?

YES !
Particles, like photons, also have a wavelength given by:

The wavelength of a particle depends on its momentum,

just like a photon!

The main difference is that matter particles have mass,

and photons don’t!
 Matter Waves
Compute the wavelength of a 10 [g] bullet moving at 1000 [m/s].

λ = h/mv = 6.6x10-34 [J s] / (0.01 [kg])(1000 [m/s])

= 6.6x10-35 [m]

This is immeasureably small

For ordinary “everyday objects,”

we don’t experience that

MATTER CAN BEHAVE AS A WAVE