Classical simulation of free-fermionic dynamics and quantum chemistry with magic input

Establishing the precise computational boundary between classically tractable fermionic systems and those capable of genuine quantum advantage is a central challenge in quantum simulation. While injecting non-Gaussian ``magic" inputs into free-fermion circuits is widely expected to generate intractable complexity, we identify a physically motivated intermediate regime. We prove that for block-product paired non-Gaussian fermionic states, essential quantum simulation primitives – transition amplitudes, overlaps, and arbitrary-weight number correlators – can be efficiently approximated to additive error under free-fermionic dynamics. This tractability stems from an algebraic reduction that compresses exponentially large multiparticle interference into a single coefficient of a multivariate Pfaffian polynomial. Because these classical estimators match the intrinsic $O(1\mathrm{/}\sqrt{K})$ statistical uncertainty of quantum hardware utilizing $K$ measurement shots, they constitute a practical benchmark. Building on this foundation, we construct an additive-error estimator for high-weight Wilson observables in the noninteracting quench of recent trapped-ion experiments, providing a rigorous classical benchmark. Extending this to quantum chemistry, we demonstrate that core overlap-based subroutines for antisymmetrized products of strongly orthogonal geminals admit efficient additive-error Pfaffian-kernel estimators. Ultimately, these results sharpen the boundary of quantum advantage, establishing that the paired-electron scaffold is dequantized and clarifying where quantum resources are indispensable.