Nonlinear polarization description of phase‐locked pulse‐pair spectroscopy

The recently demonstrated technique of optically phase‐locked pulse‐pair (PLPP) excited spontaneous emission is described by a third‐order perturbative density matrix approach. A nonlinear polarization description shows how PLPP spectroscopy depends on all the relevant material dephasing time scales. The time and frequency integrated resonance spontaneous emission consists entirely of resonance fluorescence, and is derived exclusively from excited‐state population decay terms, i.e., diagonal second‐order density‐matrix elements. These third‐order polarization results are proportional to the previously derived linear polarization expressions found to describe the observed PLPP I2 vapor emission. The nonlinear treatment allows a comparison of this technique to other forms of ultrafast pump–probe spectroscopies such as transient absorption and photon echo techniques. The role of impulsively prepared coherences is clearly described by this analysis. The effect of pulse duration, relative to material dephasing...