Theory of coherent polarization anisotropy in time-resolved two-photon ionization of isolated molecules. Effects of Coriolis couplings

Abstract

Effects of vibration–rotation (Coriolis) couplings on the coherent polarization anisotropy are theoretically studied in a time-resolved two-photon ionization of a symmetric top molecule. This polarization anisotropy originates from a coherent excitation of the resonant rovibronic molecular eigenstates (rovibronic coherence) whose zeroth order states are mixed through the Coriolis coupling. Expressions for the time-dependent degree of polarization after the coherent excitation of the rovibronic states produced by the Coriolis coupling are derived as a function of the delay time in the pump–probe two-photon ionization. Model calculations of the time-dependent degree of polarization as well as the probabilities of the two-photon ionization are performed to demonstrate the Coriolis coupling effects in the low excess energy regions of the resonant intermediate state. It is shown that oscillatory behaviors in the time-dependent degree of polarization should be observed as a result of the creation of the rovibronic coherence. It is demonstrated that oscillations of the degree of polarization involve both contribution of the purely rotational J-coherence and that of the rovibronic coherence in the resonant manifold when the rotational branches are coherently excited and the characteristic rotation–vibration interaction energy is larger than a typical free rotational energy under jet-cooled condition.