They looked for the emission of certain wavelengths within the radio part of the electromagnetic spectrum. Molecules each emit a distinctive band of radio wavelengths, which can be used as a fingerprint for the molecules.
You wait for the planet to pass through the star, that way you get the spectroscopic reading for the planet and start combined. Then you wait for the planet to pass behind the star and you get the spectroscopic reading for the star only. Then you subtract them and you get the reading for the planet.
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