Toward Accurate Calculation of Excitation Energies on Quantum Computers with ΔADAPT-VQE: A Case Study of BODIPY Derivatives.

Quantum chemistry simulations offer a cost-effective way to computationally design BODIPY photosensitizers. However, accurate predictions of excitation energies pose a challenge for time-dependent density functional theory and equation-of-motion coupled-cluster singles and doubles methods. By contrast, reliable predictions can be achieved by multireference quantum chemistry methods; unfortunately, their computational cost increases exponentially with the number of electrons. Alternatively, quantum computing holds potential for an exact simulation of the photophysical properties in a computationally more efficient way. Herein, we introduce the state-specific ΔUCCSD-VQE (unitary coupled-cluster singles and doubles-variational quantum eigensolver) and ΔADAPT-VQE methods in which the electronically excited state is calculated via a non-Aufbau configuration. We show for six BODIPY derivatives that the proposed methods predict accurate excitation energies that are in good agreement with those from experiments. Due to its performance and simplicity, we believe that ΔADAPT will become a useful approach for the simulation of BODIPY photosensitizers on near-term quantum devices.