Computing the free energy of quantum Coulomb gases and molecules via quantum Gibbs sampling

TL;DR

This paper introduces a quantum algorithm for estimating the free energy and Gibbs state of interacting quantum Coulomb gases and molecules, overcoming previous limitations due to singular interactions and infinite-dimensional spaces.

Contribution

It develops a low-rank truncation approach combined with a quantum Gibbs sampling scheme with proven exponential convergence guarantees.

Findings

Provides explicit error bounds for free energy approximation.

Establishes a spectral gap for the quantum Markov generator, ensuring rapid mixing.

Offers an explicit quantum circuit implementation with complexity bounds.

Abstract

We develop a quantum algorithm for estimating the free energy as well as the total Gibbs state of interacting quantum Coulomb gases and molecular systems in dimensions $d \in \{2,3\}$ at finite temperature. These systems lie beyond the reach of existing methods due to their singular interactions and infinite-dimensional Hilbert space structure. First, we show that the free energy of the full many-body Hamiltonian can be approximated by that of the same Hamiltonian with a finite-rank low-energy truncation of the interaction, with an explicit error bound polynomial in the particle number. This reduces the problem to a controlled finite-rank perturbation problem. Second, we introduce a quantum Gibbs sampling scheme tailored to this truncated system, based on a class of quantum Markov semigroups. Our main analytical result establishes that the associated generator has a strictly positive spectral gap for every truncation, implying exponential convergence to the target Gibbs state. This provides, to our knowledge, the first rigorous mixing-time guarantee for Gibbs sampling in a Coulomb interacting continuous-variable quantum system. Finally, we give an explicit quantum circuit implementation of the dynamics and derive an end-to-end complexity bound for approximating the free energy and the Gibbs state itself. Our results provide a mathematically rigorous route to quantum algorithms for free energy estimation in interacting quantum systems, without relying on classical approximations such as the Born-Oppenheimer reduction.