HYDROGEN ATOM AND QUANTUM

NUMBERS
Hydrogen Atom

Application of the Schrödinger

Equation to the Hydrogen Atom
Solution of the Schrödinger Equation
for Hydrogen
Quantum Numbers

Werner Heisenberg
(1901-1976)

The atom of modern physics can be symbolized only through a partial differential
equation in an abstract space of many dimensions. All its qualities are inferential; no
material properties can be directly attributed to it. An understanding of the atomic world
in that primary sensuous fashion…is impossible.
- Werner Heisenberg
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,
.
 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:
Separable Solution

The wave function is a function of r, , . This is a potentially

complicated function.

Assume instead that  is separable, that is, a product of three

functions, each of one variable only:

This would make life much simpler, and it turns out to work.
7.2: Solution of the Schrödinger
Equation for Hydrogen
Start with Schrodinger’s Equation:

Substitute:

Multiply both sides by r2 sin2 / R f g:

Solution of the Schrödinger Equation for H

r and  appear only on the left side and  appears only on the right side.
The left side of the equation cannot change as  changes.
The right side cannot change with either r or .

Each side needs to be equal to a constant for the equation to be true.

Set the constant to be −mℓ2

azimuthal equation

It is convenient to choose the solution to be .

Solution of the Schrödinger Equation for H

satisfies the azimuthal equation for any value of mℓ.

The solution must be single valued to be a valid solution for any :

Specifically:

So:

mℓ must be an integer (positive or negative) for this to be true.

 Solution of the Schrödinger Equation for H

Now set the left side equal to −mℓ2:

−mℓ2

Rearrange it and divide by sin2():

Now, the left side depends only on r, and the right side depends
only on . We can use the same trick again!
 Solution of the Schrödinger Equation for H

Set each side equal to the constant ℓ(ℓ + 1).

Radial equation

Angular equation

We’ve separated the Schrödinger equation into three ordinary second-

order differential equations, each containing only one variable.
Solution of the Radial Equation for H
The radial equation is called the associated Laguerre equation and the
solutions R are called associated Laguerre functions. There are
infinitely many of them, for values of n = 1, 2, 3, …

Assume that the ground state has n = 1 and ℓ = 0. Let’s find this solution.
The radial equation becomes:

The derivative of yields two terms:

 Solution of the Radial Equation for H
Try a solution
A is a normalization constant.
a0 is a constant with the dimension of length.
Take derivatives of R and insert them into the radial equation.

To satisfy this equation for any r, both expressions in parentheses must be zero.

Set the second expression

equal to zero and solve for a0:

Set the first expression equal

to zero and solve for E:

Both are equal to the Bohr results!

Principal
Quantum
Number n

There are many solutions to the radial wave equation, one for
each positive integer, n.

The result for the quantized energy is:

A negative energy means that the electron and proton are bound
together.
Quantum Numbers

The three quantum numbers:

n: Principal quantum number
ℓ: Orbital angular momentum quantum number
mℓ: Magnetic (azimuthal) quantum number

The restrictions for the quantum numbers:

n = 1, 2, 3, 4, . . .
ℓ = 0, 1, 2, 3, . . . , n − 1
mℓ = −ℓ, −ℓ + 1, . . . , 0, 1, . . . , ℓ − 1, ℓ

Equivalently:
n>0
ℓ<n The energy levels are:
|mℓ| ≤ ℓ
 Hydrogen Atom Radial Wave Functions

First few
radial
wave
functions
Rnℓ

Sub-
scripts
on R
specify
the
values of
n and ℓ.
Solution of the Angular and Azimuthal
Equations

The solutions to the azimuthal equation are:

Solutions to the angular and azimuthal equations are linked

because both have mℓ.

Physicists usually group these solutions together into

functions called Spherical Harmonics:

spherical harmonics
Normalized
Spherical
Harmonics
Solution of the Angular and Azimuthal
Equations

The radial wave function R and the spherical harmonics Y determine the
probability density for the various quantum states. The total wave
function depends on n, ℓ, and mℓ. The wave function becomes
Probability Distribution Functions

We use the wave functions to calculate the probability

distributions of the electrons.

The “position” of the electron is spread over space and is not

well defined.

We may use the radial wave function R(r) to calculate radial

probability distributions of the electron.

The probability of finding the electron in a differential volume

element dis:
 Probability Distribution Functions
The differential volume element in spherical polar coordinates is

Therefore,

At the moment, we’re only interested in the radial dependence.

The radial probability density is P(r) = r2|R(r)|2 and it depends only on n and
ℓ.
Probability
Distribution
Functions

R(r) and P(r)

for the lowest-
lying states of
the hydrogen
atom.
 Probability Distribution Functions
The probability density for the hydrogen atom for three different electron
states.
Orbital Angular Momentum Quantum
Number ℓ
Energy levels are degenerate with respect to ℓ (the energy is
independent of ℓ).

Physicists use letter names for the various ℓ values:

ℓ= 0 1 2 3 4 5...
Letter = s p d f g h...

Atomic states are usualy referred to by their values of n and ℓ.

A state with n = 2 and ℓ = 1 is called a 2p state.

Orbital Angular Momentum Quantum
Number ℓ
It’s associated with the R(r) and f(θ) parts of the wave function.

Classically, the orbital angular momentum with L = mvorbitalr.

L is related to ℓ by

In an ℓ = 0 state,

This disagrees with Bohr’s

semi-classical “planetary”
model of electrons orbiting
a nucleus L = nħ. Classical orbits—which do not
exist in quantum mechanics
 Magnetic Quantum
The solution for g() specifies that Number mℓ
mℓ is an integer and is related to
the z component of L:

Example: ℓ = 2:

Only certain orientations of are

possible. This is called space
quantization.

And (except when ℓ = 0) we just

don’t know Lx and Ly!