The emission spectrum of a chemical element or chemical compound is the spectrum of frequencies of electromagnetic radiation emitted by the atom's electrons when they are returned to a lower energy state. Each element's emission spectrum is unique; therefore, spectroscopy can be used to identify the elements in matter of unknown composition. Similarly, the emission spectra of molecules can be used in chemical analysis of substances.
The emission spectrum of atomic hydrogen is divided into a number of spectral series , with wavelengths given by the Rydberg formula:
where R is the Rydberg constant (approximately 1.09737 x 107 m-1),
The spectral lines are grouped into series according to n′. Lines are named sequentially starting from the longest wavelength/lowest frequency of the series, using Greek letters within each series. For example, the 2 → 1 line is called "Lyman-alpha" (Ly-α), while the 7 → 3 line is called "Paschen-delta" (Pa-δ). Some hydrogen spectral lines fall outside these series, such as the 21 cm line; these correspond to much rarer atomic events such as hyperfine transitions. The fine structure also results in single spectral lines appearing as two or more closely grouped thinner lines, due to relativistic corrections. Typically one can only observe these series from pure hydrogen samples in a lab. Many of the lines are very faint and additional lines can be caused by other elements (such as helium if using sunlight, or nitrogen in the air). Lines outside of the visible spectrum typically cannot be seen in observations of sunlight, as the atmosphere absorbs most infra-red and ultraviolet wavelengths.
The collection of series, tabulated and referenced to the transition number, can be seen in .