Modal Backflow Neural Quantum States for Anharmonic Vibrational Calculations

Abstract

Neural quantum states (NQS) are a promising ansatz for solving many-body quantum problems due to their inherent expressiveness. Yet, this expressiveness can only be harnessed efficiently for treating identical particles if the suitable physical knowledge is hardwired into the neural network itself. For electronic structure, NQS based on backflow determinants has been shown to be a powerful ansatz for capturing strong correlation. By contrast, the analogue for bosons, backflow permanents, is unpractical due to the steep cost of computing the matrix permanent and due to the lack of particle conservation in common bosonic problems. To circumvent these obstacles, we introduce a modal backflow (MBF) NQS design and demonstrate its efficacy by solving the anharmonic vibrational problem. To accommodate the demand of high accuracy in spectroscopic calculations, we implement a selected-configuration scheme for evaluating physical observables and gradients, replacing the standard stochastic approach based on Monte Carlo sampling. A vibrational self-consistent field calculation is conveniently carried out within the MBF network, which serves as a pretraining step to accelerate and stabilize the optimization. In applications to both artificial and ab initio Hamiltonians, we find that the MBF network is capable of delivering spectroscopically accurate zero-point energies and vibrational transitions in all anharmonic regimes.