Accidental degeneracy beats: A distinct type of beat phenomenon in nonlinear optical spectroscopy

A type of beat in nonlinear optical spectroscopy that is distinct from quantum beats (QB's) and polarization beats, is described. Like a quantum beat, this beat, which we refer to as an accidental degeneracy beat (ADB), can only be seen in multilevel systems. However, unlike quantum beats, which are the result of intramolecular interferences, ADB's are interferences between different subensembles of molecules in the sample. They require multilevel systems with spectral overlap. ADB's can appear as separate frequencies or as phase and amplitude contributions with the same frequency as that of quantum beats. A procedure for distinguishing between quantum beats and ADB's is outlined, and criteria under which ADB's are expected to be observed are delineated. Calculations of the spectrally resolved stimulated vibrational echo signal from an inhomogeneously broadened coupled anharmonic oscillator system are presented to illustrate the differences between the two types of beats. ADB's carry information about the anharmonicity of a system, while QB's carry information about intramolecular correspondence of transition frequencies in a multilevel system.