Polaritonic Unitary Coupled Cluster for Quantum Computations

Abstract: In the field of polaritonic chemistry, strong light-matter interactions are used to alter a chemical reaction inside an optical cavity. To explain and understand these processes, the development of reliable theoretical models is essential. While traditional methods have to balance accuracy and system size, new developments in quantum computing, in particular the Variational Quantum Eigensolver (VQE), offer a path for an accurate solution of the electronic Schr\"odinger equation with the promise of polynomial scaling and eventual quasi-exact solutions on currently available quantum devices. In this work, we combine these two fields. In particular, we introduce the quantum electrodynamics unitary coupled cluster (QED-UCC) method combined with the VQE algorithm, as well as the quantum electrodynamics equation-of-motion (QED-EOM) method formulated in the qubit basis that allows an accurate calculation of the ground-state and the excited-state properties of strongly coupled light-matter systems on a quantum computer. The accuracy and performance of the developed methods is tested for a H$_4$ molecule inside an optical cavity in a regime where strong electronic correlations become significant. For the first time, we explicitly include two photon effects from first principles. We show that the developed methods are in excellent agreement with the exact reference results and can outperform their traditional counterparts. The work presented here sets the stage for future developments of polaritonic quantum chemistry methods suitable for both classical and quantum computers.