Simulating high-accuracy nuclear motion Hamiltonians using discrete variable representation and Walsh-Hadamard QROM on fault-tolerant quantum computers

Abstract

We present a quantum algorithm for simulating rovibrational Hamiltonians on fault-tolerant quantum computers. The method integrates exact curvilinear kinetic energy operators and general-form potential energy surfaces expressed in a hybrid finite-basis/discrete-variable representation. The Hamiltonian is encoded as a unitary quantum circuit using a quantum read-only memory construction based on the Walsh-Hadamard transform, enabling high-accuracy quantum phase estimation of rovibrational energy levels and dynamics simulations. Our technique provides asymptotic reductions in both logical qubit count and T-gate complexity that are exponential in the number of atoms and at least polynomial in the total Hilbert-space size, relative to existing block-encoding techniques based on linear combinations of unitaries and variational basis representation. Compared with classical variational methods, it offers exponential memory savings and polynomial reductions in time complexity. The quantum volume required for computing the rovibrational spectrum of water can be reduced by up to 100 000 times compared with other quantum methods, increasing to at least 1 million for a classically intractable 30-dimensional (12-atom) molecular system. For this case with a six-body coupled potential, estimating spectroscopic-accuracy energy levels would require about three months on a 1 MHz fault-tolerant quantum processor with fewer than 300 logical qubits, versus over 30 000 years on the fastest current classical supercomputer. These estimates are approximate and subject to technological uncertainties, and realizing the asymptotic advantage will require substantial quantum resources and continued algorithmic progress.