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arXiv:2111.10282 · Letters in Mathematical Physics

Two-sided Bogoliubov inequality to estimate finite size effects in quantum molecular simulations

Benedikt M. Reible, Carsten Hartmann, Luigi Delle Site

Published Sep 21, 2022• 6 citations
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Abstract

Abstract We generalise the two-sided Bogoliubov inequality for classical particles (Delle Site et al. in J Stat Mech Theory Exp 083201, 2017 to systems of quantum particles. As in the classical set-up, the inequality leads to upper and lower bounds for the free energy difference associated with the partitioning of a large system into smaller, independent subsystems. From a thermodynamic modelling point of view, the free energy difference determines the finite size correction needed to consistently treat a small system as a representation of a large system. Applications of the bounds to quantify finite size effects are ubiquitous in physics, chemistry, material science, or biology, to name just a few; in particular, it is relevant for molecular dynamics simulations in which a small portion of a system is usually taken as representative of the idealized large system.

DOI
10.1007/s11005-022-01586-3

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Abstract We generalise the two-sided Bogoliubov inequality for classical particles (Delle Site et al. in J Stat Mech Theory Exp 083201, 2017 to systems of quantum particles. As in the classical set-up, the inequality leads to upper and lower bounds for the free energy difference associated with the partitioning of a large system into smaller, independent subsystems. From a thermodynamic modelling point of view, the free energy difference determines the finite size correction needed to consistently treat a small system as a representation of a large system. Applications of the bounds to quantify finite size effects are ubiquitous in physics, chemistry, material science, or biology, to name just a few; in particular, it is relevant for molecular dynamics simulations in which a small portion of a system is usually taken as representative of the idealized large system.
We generalise the two-sided Bogoliubov inequality for classical particles from [L. Delle Site et al., J.Stat.Mech.Th.Exp. 083201 (2017)] to systems of quantum particles. As in the classical set-up, the inequality leads to upper and lower bounds for the free energy difference associated with the partitioning of a large system into smaller, independent subsystems. From a thermodynamic modelling point of view, the free energy difference determines the finite size correction needed to consistently treat a small system as a representation of a large system. Applications of the bounds to quantify finite size effects are ubiquitous in physics, chemistry, material science, or biology, to name just a few; in particular it is relevant for molecular dynamics simulations in which a small portion of a system is usually taken as representative of the idealized large system.
Finite-size effects arise when a sample of particles is not sufficient to provide a statistically satisfactory description of the bulk environment of a physical system. As a consequence, a reliable estimate of finite-size effects in many-particle systems is key to judge the validity of a theoretical model or the accuracy of a numerical simulation. In this context, we propose the use of a theorem on the free-energy cost for separating a system into smaller independent subsystems [J. Stat. Mech.: Theory Exp. (2017) 083201; Lett. Math. Phys. 112, 97 (2022)] to estimate the relevance of finite-size effects in thermodynamic quantities from computer simulations. The key aspect of this study is that for two-body potentials, as mostly occurring in physics, the method requires only two-body distribution functions and the particle number density. The calculation of the involved physical quantities can be done numerically on a three-dimensional grid. In some cases even analytical estimates are possible and as an example the uniform interacting electron gas in the ground state is considered; we derive an approximating scaling law for the finite-size effects.
The quantum-mechanical two-sided Bogoliubov inequality provides upper and lower bounds for the free energy required to separate a system of interacting particles into independent subsystems. The bounds can be calculated straightforwardly from the ensemble average of the interface energy, bypassing the direct evaluation of the free energy. In this work, we generalize the two-sided Bogoliubov inequality to arbitrary von Neumann algebras by employing the Araki-Uhlmann relative entropy and the framework of unbounded perturbation theory of KMS states. Furthermore, we obtain variational expressions for the relative free energy that extend existing bounded-perturbation principles to the unbounded setting. Crucially, these mathematical developments yield a physically well-founded thermodynamic criterion for the quantification of entanglement in infinite-dimensional systems.
In a recent work [Reible et al., Phys. Rev. Res. 5, 023156 (2023)], it was shown that the mean particle-particle interaction across an ideal surface that divides a system into two parts can be employed to estimate the size dependence for the thermodynamic accuracy of the system. In this work we propose its application to systems with finite-range interactions that model dense quantum gases and derive an approximate size-dependence scaling law. In addition, we show that the application of the criterion is equivalent to the determination of a free-energy response to a perturbation. The latter result confirms the complementarity of the criterion to other estimates of finite-size effects based on direct simulations and empirical structure or energy convergence criteria.
Hybrid quantum-classical algorithms have begun to leverage quantum devices to efficiently represent many-electron wavefunctions, enabling early demonstrations of molecular simulations on real hardware. A key prerequisite for scalable quantum chemistry, however, is size consistency: the energy of non-interacting subsystems must scale linearly with system size. While many algorithms are theoretically size-consistent, noise on quantum devices may couple nominally independent subsystems and degrade this fundamental property. Here, we systematically evaluate size consistency on quantum hardware by simulating systems composed of increasing numbers of non-interacting H2_{2}2​ molecules using optimally shallow unitary circuits. We find that molecular energies remain size-consistent within chemical accuracy for an estimated 118 and 71 H2_{2}2​ subsystems for one- and two-qubit unitary designs, respectively, demonstrating that current quantum devices preserve size consistency over chemically relevant system sizes and supporting the feasibility of scalable, noise-resilient simulation of strongly correlated molecules and materials.