Investigation of photoassociation with full-dimensional thermal-random-phase wavefunctions

By taking the femtosecond two-photon photoassociation (PA) of magnesium atoms as an example, we propose a method to calculate the thermally averaged population, which is transferred from the ground X¹Σ_g ⁺ state to the target (1)¹Π_g state, based on the solution of full-dimensional time-dependent Schrödinger equation. In this method, named as method A, we use thermal-random-phase wavefunctions with the random phases expanded in both the vibrational and rotational degrees of freedom to model the thermal ensemble of the initial eigenstates. This method is compared with the other two methods (B and C) at different temperatures. Method B is also based on thermal-random-phase wavefunctions, except that the random-phase expansion is merely used for the vibrational degree of freedom. Method C is based on the independent propagation of every initial eigenstate, instead of the thermal-random-phase wavefunctions. Taking the (1)¹Π_g state as the target state, it is found that although these three methods can present the same population on the (1)¹Π_g state, the computation efficiency of method A increases dramatically with the increase in temperature. With this efficient method A, we find that the PA process at 1000 K can also induce rotational coherence, i.e., the molecular field-free alignment in the excited electronic states.