Microwave spectroscopy is the spectroscopy method that employs microwaves, i.e. electromagnetic radiation at GHz frequencies, for the study of matter.

The ammonia molecule NH₃ is shaped like a pyramid 0.38 Å in height, with an equilateral triangle of hydrogens forming the base.The nitrogen situated on the axis has two equivalent equilibrium positions above and below the triangle of hydrogens, and this raises the possibility of the nitrogen tunneling up and down, through the plane of the H-atoms. In 1932 Dennison et al. ... analyzed the vibrational energy of this molecule and concluded that the vibrational energy would be split into pairs by the presence of these two equilibrium positions. The next year Wright and Randall observed ... a splitting of 0.67 cm^–1 in far infrared lines, corresponding to a frequency of 20 GHz, the value predicted by theory. In 1934 Cleeton and Williams ... constructed a grating echelle spectrometer in order to measure this splitting directly, thereby beginning the field of microwave spectroscopy. They observed a somewhat asymmetric absorption line with a maximum at 24 GHz and a full width at half height of 12 GHz.^[1]

In the field of molecular physics, microwave spectroscopy is commonly used to probe the rotation of molecules.^[2]

In the field of condensed matter physics, microwave spectroscopy is used to detect dynamic phenomena of either charges or spins at GHz frequencies (corresponding to nanosecond time scales) and energy scales in the µeV regime. Matching to these energy scales, microwave spectroscopy on solids is often performed as a function of temperature (down to cryogenic regimes of a few K or even lower)^[3] and/or magnetic field (with fields up to several T). Spectroscopy traditionally considers the frequency-dependent response of materials, and in the study of dielectrics microwave spectroscopy often covers a large frequency range. In contrast, for conductive samples as well as for magnetic resonance, experiments at a fixed frequency are common (using a highly sensitive microwave resonator),^[4] but frequency-dependent measurements are also possible.^[5]