Folded Spectrum VQE : A quantum computing method for the calculation of molecular excited states

Abstract: The recent developments of quantum computing present potential novel pathways for quantum chemistry, as the increased computational power of quantum computers could be harnessed to naturally encode and solve electronic structure problems. Theoretically exact quantum algorithms for chemistry have been proposed (e.g. Quantum Phase Estimation) but the limited capabilities of current noisy intermediate scale quantum devices (NISQ) motivated the development of less demanding hybrid algorithms. In this context, the Variational Quantum Eigensolver (VQE) algorithm was successfully introduced as an effective method to compute the ground state energy of small molecules. The current study investigates the Folded Spectrum (FS) method as an extension to the VQE algorithm for the computation of molecular excited states. It provides the possibility of directly computing excited states around a selected target energy, using the same ansatz as for the ground state calculation. Inspired by the variance-based methods from the Quantum Monte Carlo literature, the FS method minimizes the energy variance, thus requiring a computationally expensive squared Hamiltonian. We alleviate this potentially poor scaling by employing a Pauli grouping procedure, identifying sets of commuting Pauli strings that can be evaluated simultaneously. This allows for a significant reduction of the computational cost. We apply the FS-VQE method to small molecules (H$_2$,LiH), obtaining all electronic excited states with chemical accuracy on ideal quantum simulators.