Perturbation-theory approach for predicting vibronic selectivity by entangled-photon-pair absorption

TL;DR

This paper develops an analytical perturbation theory approach to predict vibronic selectivity in diatomic molecules excited by entangled photons, offering physical insights and computational efficiency over previous numerical methods.

Contribution

It introduces a new analytical approximation for vibronic populations excited by entangled photons, revealing how photon correlations enhance vibrational selectivity.

Findings

Analytical expression matches numerical solutions.

Photon entanglement enhances vibrational selectivity.

Vibrational structure influences quantum enhancement.

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 makes 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.