Predicting and Controlling Entangled Two-Photon Absorption in Diatomic Molecules.

The use of nonclassical states of light to probe organic molecules has received great attention due to the possibility of providing new and detailed information regarding molecular excitations. Experimental and theoretical results have been reported which show large enhancements of the nonlinear optical responses in organic materials due to possible virtual-electronic-state interactions with entangled photons. In order to predict molecular excitations with nonclassical light, more detailed investigations of the parameters involved must be carried out. In this report we investigate the details of the state-to-state parameters important in calculating the contribution of particular transitions involved in the entangled two-photon absorption process for diatomic molecules. The theoretical discussion of the entangled two-photon process is described for a set of diatomic molecules. Specifically, we provide detailed quantum chemical calculations which give accurate energies and transition moments for selection-rule allowed intermediate states important in the entangled nonlinear effect for the diatomic molecules. These results are used to estimate in a more accurate manner the nonmonotonic behavior of the entangled two-photon absorption cross-section. We also derive accurate approximations that can be used to predict the period between entanglement-induced transparencies without needing exact values of the transition dipole moments. These results suggest that with the additional parameters allotted by the entangled two-photon absorption (in comparison to the classical case), it may be possible to predict and later control the nonlinear absorption and transparency of a molecule at a constant incident photon frequency.