Quantum particle simulations have largely been based on time-independent, split-operator schemes in which kinetic and potential operators are interwoven to provide accurate approximations to system dynamics. These simulations can be very expensive in terms of the number of gates required, although individual cases, such as tunneling, have been found where prethreshold simulations are possible. By prethreshold, we mean a quantum computation or simulation with an existing architecture and not requiring error correction. In the case of molecular collisions, switching to a time-dependent formulation can reduce the system dimensionality significantly and provide an opportunity for pre-threshold simulation. Here, we study the efficiency of gate-based quantum simulation of a set of molecular collisions of increasing complexity. We show that prethreshold quantum simulation of such systems is feasible up to Hilbert space dimension 8, but beyond that error correction would be required.
In the study of non-adiabatic chemical processes such as photocatalysis and photosynthesis, non-adiabatic molecular dynamics (NAMD) is an indispensable theoretical tool, which requires precise potential energy surfaces (PESs) of ground and excited states. Quantum computing offers promising potential for calculating PESs that are intractable for classical computers. However, its realistic application poses significant challenges to the development of quantum algorithms that are sufficiently general to enable efficient and precise PES calculations across chemical systems with diverse properties, as well as to seamlessly adapt existing NAMD theories to quantum computing. In this work, we introduce a quantum-adapted extension to the Landau-Zener-Surface-Hopping (LZSH) NAMD. This extension incorporates curvature-driven hopping corrections that protect the population evolution while maintaining the efficiency gained from avoiding the computation of non-adiabatic couplings (NACs), as well as preserving the trajectory independence that enables parallelization. Furthermore, to ensure the high-precision PESs required for surface hopping dynamics, we develop a sub-microhartree-accurate PES calculation protocol. This protocol supports active space selection, enables parallel acceleration either on quantum or classical clusters, and demonstrates adaptability to diverse chemical systems - including the charged H3+ ion and the C2H4 molecule, a prototypical multi-reference benchmark. This work paves the way for practical application of quantum computing in NAMD, showcasing the potential of parallel simulation on quantum-classical heterogeneous clusters for ab-initio computational chemistry.
The single excitation subspace (SES) method for universal quantum simulation is investigated for a number of diatomic molecular collision complexes. Assuming a system of
n tunably-coupled, and fully-connected superconducting qubits, computations are performed in the
n-dimensional SES which maps directly to an
n-channel collision problem within a diabatic molecular wave function representation. Here we outline the approach on a classical computer to solve the time-dependent Schrödinger equation in an
n-dimensional molecular basis - the so-called semiclassical molecular-orbital close-coupling (SCMOCC) method - and extend the treatment beyond the straight-line, constant-velocity approximation which is restricted to large kinetic energies (
≳0.1 keV/u). We explore various multichannel potential averaging schemes and an Ehrenfest symmetrization approach to allow for the application of the SCMOCC method to much lower collision energies (approaching 1 eV/u). In addition, a computational efficiency study for various propagators is performed to speed-up the calculations on classical computers. These computations are repeated for the simulation of the SES approach assuming typical parameters for realistic pretheshold superconducting quantum computing hardware. The feasibility of applying future SES processors to the quantum dynamics of large molecular collision systems is briefly discussed.