HYDROGEN ATOM WAVE FUNCTIONS

The hydrogen atom is the simplest atom consisting of one electron and one proton. The time-
independent form of Schrodinger equation is HΨ = EΨ. The Hamiltonian operator consists of
two terms, i.e., the kinetic energy term and the potential energy terms. The potential energy, V,
of the coulombic interaction between the nucleus of charge +e and the electron of charge –e is

V = Q1Q2 /4πε0r, with Q1 = Ze = e (For hydrogen, Z = 1) and Q2 = -e

𝑒2
i.e., V = - where 𝜀0 =8.854 X 10-12 J-1C2m-1 is the vacuum permittivity. The negative sign
4πε0 𝑟
indicates that the potential energy falls 9becomes more negative) as the distance between the
nucleus and the electron decreases. The Schrodinger equation for the hydrogen atom can then
be written as

𝝏𝟐 Ψ 𝝏𝟐 Ψ 𝝏𝟐 Ψ 𝟖𝛑𝟐 𝒎 𝑒2
+ + + (E + )Ψ =0
𝝏𝒙𝟐 𝝏𝒚𝟐 𝝏𝒛𝟐 𝒉𝟐 4πε0 𝑟

This equation can be solved by transforming the Cartesian coordinates into spherical
coordinates r, θ and φ (PHI), as shown in the figure

The wave function Ψ (x,y,z) can be expressed as the product of two functions, one of which (the
angular part Υ or upsilon) depends only on the angles θ and Φ the other of which ( the radial
part R) depends only on the distance from the nucleus. Thus, we have

Ψ(r, θ, Φ) = R(r) Υ (θ, ϕ)

The Schrodinger equation after transformation into spherical coordinates takes the form

1 𝜕 𝜕𝜓 1 𝜕𝜓 1 𝜕2 𝜓 8π2 𝑚 𝑒2
( r2 )+ 𝑠𝑖𝑛2θ( sinθ 𝜕𝜃 ) + 𝑠𝑖𝑛2 𝜃 + (E + )Ψ =0
𝑟 2 𝜕𝑟 𝜕𝑟 𝑟2 𝑟2 𝜕𝜙2 ℎ2 4πε0 𝑟

On solving this equation, we get three ordinary differential equations. Each of these differential
equations on solving leads to the emergence of three quantum numbers.

1. The principal quantum number, n : This a number that can assume any positive integral
value, excluding zero. Its value determines the energy of the hydrogen atom by the formula

𝑚𝑒 4 𝑍 2
E= - Where m and e are the mass and charge of electron, Z atomic number, ℏ
8𝜀02 𝑛2 ℏ2
ℎ
reduced Planck’s constant (2π).

2. The orbital angular momentum quantum number or Azimuthal quantum number, l

The value of l determines the angular momentum of the electron. It may assume all integral
values from 0 to n-1. i.e., 0, 1 …., n-2, n-1.

3.The orbital magnetic quantum number, m.

The value of m indicates the magnetic field associated with the circulating electron. m can
assume all integral values between –l and +l, including zero. That is m can have 2l+1 values of

–l, -l+1, …, 0, 1, ….,. l.

4. The electron has a spin angular momentum due its spinning about its own axis. The magnetic
quantum number associated with this spin has two possible values, + ½ and – ½.

Since the value of n restricts the possible values of l, and the value of l in turn restricts
the allowed values of m, only certain combinations of quantum numbers are possible. In
general, the number of possible combinations of quantum numbers all with the same value of n
is 2n2. Each set of quantum numbers is associated with a different type of electronic motion.
Each possible combination of quantum numbers represents various possible types of orbital.
 The orbitals are classified according to the values n and l associated with them. To avoid
confusion over use of two numbers, the numerical values of l are replaced by letters: electrons
in orbitals with l=0 are called s electrons, those electrons occupying orbitals for which l=1 are p
electrons, ad those for which l=2 are called d electrons. The numerical and alphabetical
correspondences are summarized in the table below:

Using the alphabetical notation for l, we can say that in the ground state of the hydrogen atom
(n=1, l=0) we have 1s electron or that the electron moves in a 1s orbital.
Forms of hydrogen atom wave functions

The wave function ψ for the electron in hydrogen atom can be expressed as the product of two
functions as

Ψ(r, θ, Φ ) = R(r) Υ (θ, ϕ )

The table shown below contains the expressions for the angular and radial parts of the one-
electron –atom wave functions. Note that the angular part of the wave function for an s orbital
is always the same, (1/4π)1/2, regardless of principal quantum number. Thus, all orbitals of a
given type (s, p, or d) have the same angular behavior. The radial part of the wave function,
however, depends both on the principal quantum number n and on the angular momentum
quantum number l.
To find the wave function for a particular orbital, we simply multiply the appropriate angular
and radial parts together.

Wave function for 1s orbital

For the ground state, n=1, and l=0, m=0, Such an orbital is called 1s orbital. It depends only on
the radial coordinate (r) and is independent of θ and φ. The normal wave function for 1s orbital
in the ground state is given below:

1
Ψ= (1/𝑎0 )3/2𝑒 − 𝑟/𝑎0
√𝜋

ℎ2 (4𝜋𝜀0 )
where a0 = = 0.529 X 10 – 8 cm (Bohr radius)
4𝜋2 𝑚𝑒 2

By squaring this function, we obtain an expression for the probability of finding the electron in
a unit volume as a function of r, the distance from the nucleus. Thus, the probability of finding
an electron in a 1s orbital is independent of the angular coordinates θ and φ.
Wave function for 2s orbital

When n=2 and l= 0, the orbital is the 2s orbital and it has the wave function
𝑟
1 1 𝑟 −
Ψ (2s) = ( )3/2 (2- )𝑒 2𝑎0
4√2𝜋 𝑎0 𝑎0

𝑟
in the exponential factor shows that as r increases, the 2s function decreases in
2𝑎0
𝑟
amplitude more slowly than does the 1s function, which has in its exponential factor.
𝑎0

𝑟
When r = 2a0, the factor (2- ) becomes zero and hence the wave function ψ is zero. That is
𝑎0

r = 2a0 is the condition for a radial node, i.e., the radius at which the probability of finding an
electron is zero.

Similarly, on analyzing the wave function for 3s orbital it can be shown that there are two radial
nodes for 3s orbital. In general, fr an ns orbital, there are n-1 radial nodes.

Wave function for 2p orbital

When n=2 and l=1, we have p orbitals. The wave function for p orbital is dependent on θ and φ
and hence p orbitals have marked directional character. For states l=1, m can be -1, 0, +1.
Different values of m correspond to orbitals of different orientation of orbital angular
momentum. The normalized wave function for the pz orbital (the orbital having zero
component of angular momentum about z axis) can be expressed as
𝑟
11 𝑟 −
Ψ (2pz ) = ( )3/2 𝑒 2𝑎0 cos θ
4√2𝜋 𝑎0 𝑎0

In contrast to the s orbital wave functions, which were nonzero at r= 0, the p orbital wave
functions vanish at r= 0. Thus it can be said that s electron has the ability to penetrate to the
nucleus while the p electrons get close to the nucleus but does not penetrate to it. Again, in
contrast to s orbitals, the p orbitals are not spherically symmetric, but have directional
character due to the angular part of the 2p wave function. Since ψ (2pz) is proportional to cos θ,
it has maximum positive value along the positive z axis, for there θ= 0, and cos 0 = 1, which is
the maximum value of cosine. Similarly, along the negative z axis the 2pz function has its most
negative value, for there, θ= π, and cosπ= - 1, the most negative value of the cosine.

Radial probability distribution

The amplitude or intensity of three-dimensional electron wave, known as Wavefunction is

represented by ψnlm (r,θ, Φ). It has both radial and angular parts.
ψnlm (r,θ, Φ) = Radial part x Angular part = Rnl(r) x Φlm(θ, Φ)
where,
Rnl(r) = Radial wavefunction
Φlm(θ, Φ) = Angular wavefunction

Radial probability density: The square of the radial wavefunction is known as radial
probability density.

Radial probability density = |R|2

It gives the probability of finding the electron at one particular point at a distance r from the
nucleus

Radial probability distribution or Radial probability function:

It is the probability of finding the electron anywhere in a spherical shell enclosed between a
sphere of radius 'r + dr' and a sphere of radius "r' from the nucleus.
 The relation between radial probability distribution and radial probability density is given as:
Radial Probability distribution = Radial Probability Density x Volume of spherical shell =
4πr2drR2
= 4πr2R2 when dr =1

Plots of hydrogen atom wave functions OR Radial probability distribution curve

Radial probability distribution curve gives idea about the distribution of electron density at a
radial distance around the nucleus without considering the direction or angle. The plots given
below show how the radial probability (4πr2R2 or ψ2r2) depends on the distance from the
nucleus for various orbitals.
The maxima in the radial probability curves occur at radii at which the electron is most likely to
be found. For the 1s electron of the hydrogen atom, this radius of maximum probability is equal
to a0 (Bohr radius = 0.529 X 10 – 8 cm). The curves show that on average the 2s electrons spends
its time a greater distance from the nucleus than does a 1s electron. This is consistent with the
relative energies of the 1s and 2s states, because the electron that is closer to the nucleus is
bound to have the lower energy. Comparison of the radial probability curves of of electrons
with the same value of n but different values of l shows that the average distance of such
electrons from the nucleus is approximately the same. However, an s electron has a greater
chance of being very close to the nucleus than does a p electron.