III. Quantum Numbers (5.

52–62)

Using the “old” quantum theory, we have seen that the hydrogen atom has
certain discrete energy states (“orbits”) associated with it. As it turns out, “orbits”
really don’t exist, even in the hydrogen atom. In 1925, Bohr’s quantum theory was
superceded by the new quantum mechanics which also predicted discrete states for the
hydrogen atom, but with a bit more complexity. In quantum mechanics, the system
(say, for example, the hydrogen atom) is described using a mathematical formula called
Schrödinger’s equation. When this equation is solved for the system (again, the H atom
for example), it leads to an infinite number of solutions. Each solution is a
mathematical function, and each solution can be described by a set of four quantum
numbers. Each solution to Schrödinger’s equation also represents a state of the system.
In the case of the hydrogen atom, this means an energy state that the electron can exist
in. These states, these mathematical functions that are solutions to Schrödinger’s
equation, are called atomic orbitals, and they are characterized by the four quantum
numbers mentioned a moment ago. Without trying to prove where these numbers
come from, let’s write them down and see what properties they have. (And ultimately
see how they lead to the periodic table!)

A. The Principal Quantum Number: (n = 1, 2, 3,…)

The principal quantum number, n, is a measure of the size and energy of an

orbital (again, an energy state that an electron occupies) – the larger n is, the larger the
orbital, and the more energy it has. n can take on integer values of 1 or 2 or 3, etc. up to
infinity.

B. The Angular Momentum Quantum Number: (l = 0, 1, 2, …, n – 1.)

The angular momentum quantum number, l, tells us what the shape of the
orbital is. This quantum number depends on the principal quantum number; that is, if
n is 2, then l can be 0 or 1. If n is 3, then l can be 0, 1, or 2. In general, l can be 0, 1, 2, etc.,
up to n – 1.

Specific values of l are given letter-names: if l = 0, this is called an “s” orbital. If l

= 1, it is a “p” orbital, etc. The names are summarized below:

l 0 1 2 3 4 5 6
name of
s p d f g h i
orbital

An orbital is usually named by referring to its principal and angular momentum

quantum numbers. For example, if an orbital has n = 2 and l = 1, it is called a “2p”
orbital. If an orbital has n = 3 and l = 2, it is called a “3d” orbital, etc. We will return to
orbital shapes in a moment…

C. The Magnetic Quantum Number: (ml = -l, -l +1, …, 0, …, l – 1, l.)

 The magnetic quantum number describes the orientation in space of the orbital.
Just as l depends on n, ml depends on l. ml can take on values of –l, –l +1, …, 0, …, l – 1,
l. For example, a 3p orbital can have ml values of –1, 0, or 1. A 3d orbital can have ml
values of –2, –1, 0, 1, or 2. So, since ml describes the orientation of orbitals, this means
there are three 3p orbitals, each oriented a different direction in space. There are five 3d
orbitals, etc.

D. The Electron Spin Quantum Number (ms = + 12 ,– 12 )

Not all electrons are created equal. If you pass a stream of electrons through a
magnetic field, roughly half will be deflected one direction, the other half the opposite
direction. This can be accounted for if we assign
! a spin to the electron. (You shouldn’t
think of this as a spherical electron spinning on its axis—after all, an electron has both
particle character and wave character—but it is a fairly good analogy.) An electron can
be either spin-up (ms = 1/2) or spin-down (ms = –1/2).

IV. Atomic Orbitals (5.66–70)

So we’ve seen that orbitals can be classified according to the following scheme:

n=1 n=2

l=0 l=0 l=1

ml = 0 ml = 0 ml = –1 ml = 0 ml = +1

ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12

And in a slightly different format for n = 3…

! ! ! ! !
n= 3

l=0 l=1 l=2

ml = 0 ml = "1 ml = 0 ml = +1 ml = "2 ml = "1 ml = 0 ml = +1 ml = +2

ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12

Using this scheme as a guide, let’s consider s, p, and d orbitals separately:

! A. s Orbitals
 s orbitals correspond to an angular momentum quantum
number of l = 0. We mentioned earlier that l carries information
about the shape of an orbital. In principle, orbitals extend from
the nucleus of the atom out to infinity, but there is only a very
small chance of the electron being infinitely separated from the
nucleus. If we plot the three-dimensional region where there’s,
say, a 90% chance that the electron is there, this is called a
boundary surface diagram, and it betrays the shape of the orbital.
(A boundary surface diagram is shown above.) An s orbital is An s orbital
perfectly spherical. A 2s orbital is larger and has more energy
than a 1s, but they both are spherical. (Recall that the principal quantum number tells
us about the size and energy of the orbital.) Refer to the diagram above: for n = 1, l can
only equal 0, so it is an 1s orbital. when l is zero, ml can only be zero, so there is only
one orientation of the orbital (which makes sense, since any way we turn a sphere it
looks the same). Within that 1s orbital, there can be two electrons: one spin-up (ms =
1/2) and the other spin-down (ms = –1/2).

a px orbital a py orbital a pz orbital

The three p orbitals. Note: they all have the same shape!
(The different colors refer to a change in sign of the orbitals; orbitals are really just mathematical
functions. We will not discuss this idea in this particular course.)

B. p Orbitals

When n = 2, then l can be 0 or 1. If it’s zero, we have an s orbital, discussed

above. If l = 1, we have a p orbital, and from the diagram above, a p orbital can have
three orientations, corresponding to ml = –1, 0, or 1. All three p orbitals are the same
“dumbbell” shaped, but they can be orientated along each of the three Cartesian
directions, hence the three ml values. The three p orbitals are called px, py, and pz,
depending on which axis they align with. Within each of the three p orbitals, there can
be two electrons; one spin-up, the other spin-down. With this terminology, we can
rewrite the n = 2 diagram as follows:
 n=2

s p

ml = 0 ml = "1 ml = 0 ml = +1

ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12

So we have the 2s orbital, capable of holding two electrons, and the 2px, 2py, and 2pz
orbitals, capable of holding a total of six electrons. This means there is room for a grand
total of eight electrons
! in the n = 2 shell.

C. d Orbitals

From the initial diagram above, you can see that there’s five orientations of the l
= 2, or d orbitals. The five orbitals are given the following names, depending on their
orientation: xy, xz, yz, x2-y2, and z2. You can see pictures of these below. (They all have
the same 3-dimensional shape except for the dz2 .)

Using these names, we can rewrite the above diagram for the n = 3 shell with these new
monikers:

n= 3

s p d

ml = 0 x y z xy xz yz x2 " y 2 z2

ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12 ms = ± 12

Confirm for yourself that there is room for 18 electrons in the n = 3 shell.
! D. Orbital Energies

We already know that, in general, an orbital’s energy depends on its principal

quantum number – that is, a 4s orbital has more energy than a 3p, etc. For a hydrogen
atom (which only has one electron), this is true, but for many-electron systems, the
energy order changes a bit. In the many-electron case, the filling order is given by the
following sequence, from lowest energy to higher energy:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, etc…

This is easier to remember with the help of a diagram:

1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f 5g
6s 6p 6d 6f 6g 6i
7s 7p etc…

This re-ordering is due to the complex interactions between electrons in an atom, but is
easily accounted for using modern quantum chemistry, despite what is sometimes
published by people who should know better,ii who claim that quantum mechanics
cannot predict this filling order.

As electrons are added to an atom, they fill the lowest energy orbitals first. So,
the 1s will be filled before the 2s, and so on following the above order.

ii
Chemistry Quarterly American Chemical Society Newspaper, Winter 2000, p 19.