Perturbation theory scope for predicting vibronic selectivity by entangled two photon absorption

Abstract: Using second-order perturbation theory in the light-matter interaction, we derive an analytical approximation for the vibronic populations of a diatomic system excited by ultrabroadband frequency entangled photons and evaluate the population dynamics for different degrees of entanglement between photon pairs. Our analytical approach make the same predictions as previously derived via numerical solutions of the complete Schr\"odinger equation [H. Oka, Physical Review A 97, 063859 (2018)], with the added advantage of providing clear physical insights into the vibronic selectivity as a function of the degree of photon correlations while requiring significantly reduced computational effort. Specifically, our analytical expression for the probability of vibronic excitation includes a factor which predicts the enhancement of vibrational selectivity as a function of the degree correlation between the entangled photon pairs, the targeted vibrational energy level, and the vibrational molecular structure encoded in the Franck-Condon factors. Our results illustrate the importance of going beyond the usual approximations in second-order perturbation theory to capture the relevance of the vibrational structure of the molecular system of interest in order to gain a deeper understanding of the possible quantum-enhancement provided by the interaction between quantum light and matter.