Theory of lineshapes in optical–optical double resonance spectroscopy

This paper presents a theory of lineshapes for molecular Optical-Optical Double Resonance (DR) Spectroscopy with arbitrary strength for both pump and probe fields using the steady-state solutions for the 3-level density matrix. When Doppler broadening can be neglected, the results are analytical, and the probe spectrum is a pair of Lorentzian lines that display Autler-Townes splitting, each with an angular frequency half-width half maximum equal to the relaxation rates, which are assumed to be equal. When Doppler broadening is introduced, one must resort to numerical integration except for the limit of weak pump and probe fields. When the Doppler width is assumed to be much larger than the pump and probe Rabi frequencies and the probe frequency is higher than that of the pump, the calculated DR lineshapes are found to be Lorentzian with a strong pump field limit width that is proportional to the pump Rabi frequency, which is commonly known as power broadening. However, the width does not equal that Rabi frequency and is different for co- and counter-propagating pump and probe fields. Furthermore, that broadening is largely inhomogeneous, despite the Lorentzian shape. The saturation power is found to be about 4 times higher than for the bare probe transition with the same relaxation rate, dramatically lower than that expected if the width is interpreted as homogeneous.