The Rydberg formula is a mathematical formula used to predict the wavelength of light

resulting from an electron moving between energy levels of an atom.

When an electron changes from one atomic orbital to another, the electron's energy
changes. When the electron changes from an orbital with high energy to a lower energy
state, a photon of light is created. When the electron moves from low energy to a higher
energy state, a photon of light is absorbed by the atom.

Each element has a distinct spectral fingerprint. When an element's gaseous state is
heated, it will give off light. When this light is passed through a prism or diffraction
grating, bright lines of different colors can be distinguished. Each element is slightly
different from other elements. This discovery was the beginning of the study of
spectroscopy.

Rydberg Formula Equation

Johannes Rydberg was a Swedish physicist who attempted to find a mathematical
relationship between one spectral line and the next of certain elements. He eventually
discovered there was an integer relationship between the wavenumbers of successive
lines.

His findings were combined with Bohr's model of the atom to give the formula:

1/λ = RZ2(1/n12 - 1/n22)

where

λ is the wavelength of the photon (wavenumber = 1/wavelength)

R = Rydberg's constant (1.0973731568539(55) x 107 m-1)
Z = atomic number of the atom
n1 and n2 are integers where n2 > n1.

It was later found n2 and n1 were related to the principal quantum number or energy
quantum number. This formula works very well for transitions between energy levels of
a hydrogen atom with only one electron. For atoms with multiple electrons, this formula
begins to break down and give results that are incorrect. The reason for the inaccuracy is
that the amount of screening for inner electrons for outer electron transitions varies. The
equation is too simplistic to compensate for the differences.

The Rydberg formula may be applied to hydrogen to obtain its spectral lines. Setting
n1 to 1 and running n2 from 2 to infinity yields the Lyman series. Other spectral series
may also be determined:

n
n2 Converges Toward Name
1
2→
1 91.13 nm (ultraviolet) Lyman series
∞
3→
2 364.51 nm (visible light) Balmer series
∞
4→
3 820.14 nm (infrared) Paschen series
∞
5→ 1458.03 nm (far
4 Brackett series
∞ infrared)
6→ 2278.17 nm (far
5 Pfund series
∞ infrared)
7→
6 3280.56 nm (far infrared Humphreys series
∞

For most problems, you'll deal with hydrogen so you can use the formula:

1/λ = RH(1/n12 - 1/n22)

where RH is Rydberg's constant, since the Z of hydrogen is 1.

Rydberg Formula Worked Example Problem

Find the wavelength of the electromagnetic radiation that is emitted from an electron
relaxes from n = 3 to n = 1.

To solve the problem, start with the Rydberg equation:

1/λ = R(1/n12 - 1/n22)

 Now plug in the values, where n1 is 1 and n2 is 3. Use 1.9074 x 107 m-1 for Rydberg's
constant:

1/λ = (1.0974 x 107)(1/12 - 1/32)

1/λ = (1.0974 x 107)(1 - 1/9)
1/λ = 9754666.67 m-1
1 = (9754666.67 m-1)λ
1 / 9754666.67 m-1 = λ
λ = 1.025 x 10-7 m

Note the formula gives a wavelength in meters using this value for Rydberg's constant.
You'll often be asked to provide an answer in nanometers or Angstroms.
In an amazing demonstration of mathematical insight, in 1885 Balmer came up with a simple
formula for predicting the wavelength of any of the lines in atomic hydrogen in what we now
know as the Balmer series. Three years later, Rydberg generalized this so that it was possible to
determine the wavelengths of any of the lines in the hydrogen emission spectrum. Rydberg
suggested that all atomic spectra formed families with this pattern (he was unaware of Balmer's
work). It turns out that there are families of spectra following Rydberg's pattern, notably in the
alkali metals, sodium, potassium, etc., but not with the precision the hydrogen atom lines fit the
Balmer formula, and low values of n2n2 predicted wavelengths that deviate considerably.
Rydberg's phenomenological equation is as follows:

ν˜=1λ=RH(1n21−1n22)(1.5.1)(1.5.2) (1.5.1)ν~=1λ(1.5.2)=RH(1n12−1n22)
where RHRH is the Rydberg constant and is equal to 109,737 cm -1 and n1n1 and n2n2 are integers
(whole numbers) with n2>n1n2>n1.
For the Balmer lines, n1=2n1=2 and n2n2 can be any whole number between 3 and infinity. The
various combinations of numbers that can be substituted into this formula allow the calculation
the wavelength of any of the lines in the hydrogen emission spectrum; there is close agreement
between the wavelengths generated by this formula and those observed in a real spectrum.

Other Series
The results given by Balmer and Rydberg for the spectrum in the visible region of the
electromagnetic radiation start with n2=3n2=3, and n21=2n12=2. Is there a different series with
the following formula (e.g., n1=1n1=1)?
(1.5.3)1λ=RH(112−1n2)
1λ=RH(112−1n2)(1.5.3)
The values for n2n2 and wavenumber ν˜ν~ for this series would be:
Table 1.5.11.5.1: The Lyman Series of Hydrogen Emission Lines (n1=1n1=1)
n2n2 2 3 4 5 ...

λλ (nm) 121 102 97 94 ...

ν˜ν~ (cm-1) 82,2291 97,530 102,864 105,332 ...

Do you know in what region of the electromagnetic radiation these lines are? Of course, these
lines are in the UV region, and they are not visible, but they are detected by instruments; these
lines form a Lyman series. The existences of the Lyman series and Balmer's series suggest the
existence of more series. For example, the series with n22=3n22=3 and n21n12 = 4, 5, 6, 7, ... is
called Pashen series.
MULITPLE SERIES
The spectral lines are grouped into series according to n1n1 values. Lines are named sequentially
starting from the longest wavelength/lowest frequency of the series, using Greek letters within
each series. For example, the (n1=1/n2=2n1=1/n2=2) line is called "Lyman-alpha" (Ly-α), while the
(n1=3/n2=7n1=3/n2=7) line is called "Paschen-delta" (Pa-δ). The first six series have specific
names:
• Lyman series with n1=1n1=1
• Balmer series with n1=2n1=2
• Paschen series (or Bohr series) with n1=3n1=3
• Brackett series with n1=4n1=4
• Pfund series with n1=5n1=5
• Humphreys series with n1=6n1=6

The spectral series of hydrogen based of the Rydberg Equation (on a logarithmic scale).
EXAMPLE 1.5.11.5.1: THE LYMAN SERIES

The so-called Lyman series of lines in the emission spectrum of hydrogen corresponds to
transitions from various excited states to the n = 1 orbit. Calculate the wavelength of the
lowest-energy line in the Lyman series to three significant figures. In what region of the
electromagnetic spectrum does it occur?

Given: lowest-energy orbit in the Lyman series

Asked for: wavelength of the lowest-energy Lyman line and corresponding region of the
spectrum

Strategy:

1. Substitute the appropriate values into Equation RHf1.5.1RHf1.5.1 (the Rydberg equation)
and solve for λλ.

2. Locate the region of the electromagnetic spectrum corresponding to the calculated

wavelength.

Solution:

We can use the Rydberg equation (Equation 1.5.21.5.2) to calculate the wavelength:
1λ=RH(1n21−1n22)1λ=RH(1n12−1n22)
A For the Lyman series, n1=1n1=1.
1λ=RH(1n21−1n22)=1.097×m−1(11−14)=8.228×106m−11λ=RH(1n12−1n22)=1.097×m−1(11−14)=8.22
8×106m−1
Spectroscopists often talk about energy and frequency as equivalent. The cm -1 unit
(wavenumbers) is particularly convenient. We can convert the answer in part A to cm -1.

ν˜=1λ=8.228×106m−1(m100cm)=82,280cm−1ν~=1λ=8.228×106m−1(m100cm)=82,280cm−1
and

λ=1.215×10−7m=122nmλ=1.215×10−7m=122nm
This emission line is called Lyman alpha and is the strongest atomic emission line from the
sun and drives the chemistry of the upper atmosphere of all the planets producing ions by
stripping electrons from atoms and molecules. It is completely absorbed by oxygen in the
upper stratosphere, dissociating O2 molecules to O atoms which react with other
O2 molecules to form stratospheric ozone

B This wavelength is in the ultraviolet region of the spectrum.

EXERCISE 1.5.11.5.1: THE PFUND SERIES
The Pfund series of lines in the emission spectrum of hydrogen corresponds to transitions from
higher excited states to the n1=5n1=5. Calculate the wavelength of the second line in the Pfund
series to three significant figures. In which region of the spectrum does it lie?

Answer
The above discussion presents only a phenomenological description of hydrogen emission lines
and fails to provide a probe of the nature of the atom itself. Clearly a continuum model based on
classical mechanics is not applicable, and as the next Section demonstrates, a simple connection
between spectra and atomic structure can be formulated.