Multiple phase-coherent laser pulses in optical spectroscopy. II. Applications to multilevel systems

Abstract

The effects of intense laser pulse trains in coupled multilevel systems (such as pure or mixed molecular crystals) are analyzed by calculating exact density matrix evolutions. It is shown that two‐level approximations are inadequate. The contributions of exchange couplings, inhomogeneous broadening, permanent multipole interactions and transition multipole interactions to absorption and photon echo line shapes are calculated. The absorption line shape of 1,4‐dibromonaphthalene (DBN) is shown to be predominantly an isotopic substitution effect, as our Monte Carlo results give quantitative agreement with experiment for this model. Average t‐matrix approximations to the Green’s function, which have been used to propose a different mechanism for the DBN line shape are shown to be qualitatively inadequate. Dipole–dipole interactions are shown to be an important photon echo decay mechanism in mixed crystals, with the relative importance of permanent and transition multipole interactions dependent on the resonance frequency distribution. Multiple pulse trains, including multiple pulse echoes and optical multiple‐quantum sequences, are shown to be capable of distinguishing different types of interactions in the molecular Hamiltonian and reducing optical density effects. Specific pulse sequences are proposed and their effects are calculated.