The most advanced techniques using fault-tolerant quantum computers to estimate the ground-state energy of a chemical Hamiltonian involve compression of the Coulomb operator through tensor factorizations, enabling efficient block encodings of the Hamiltonian. A natural challenge of these methods is the degree to which block-encoding costs can be reduced. We address this challenge through the technique of spectral amplification, which magnifies the spectrum of the low-energy states of Hamiltonians that can be expressed as sums of squares. Spectral amplification enables estimating ground-state energies with significantly improved cost scaling in the block encoding normalization factor Λ to just 2 Λ E gap , where E gap ≪ Λ is the lowest energy of the sum-of-squares Hamiltonian. To achieve this, we show that sum-of-squares representations of the electronic structure Hamiltonian are efficiently computable by a family of classical simulation techniques that approximate the ground-state energy from below. In order to further optimize, we also develop a novel factorization that provides a trade-off between the two leading Coulomb integral factorization schemes—namely, double factorization and tensor hypercontraction—that when combined with spectral amplification yields a factor of 4 to 195 speedup over the state of the art in ground-state energy estimation for models of iron-sulfur complexes and a CO 2 -fixation catalyst.
We present sum-of-squares spectral amplification (SOSSA), a framework for improving quantum simulation relevant to low-energy problems. We show how SOSSA can be applied to problems like energy and phase estimation and provide fast quantum algorithms for these problems that significantly improve over prior art. To illustrate the power of SOSSA in applications, we consider the Sachdev-Ye-Kitaev model, a representative strongly correlated system, and demonstrate asymptotic speedups over generic simulation methods by a factor of the square root of the system size. Our results reinforce those observed in [G. H. Low et al., arXiv:2502.15882], where SOSSA was used to achieve state-of-the-art gate costs for phase estimation of real-world quantum chemistry systems.
Quantum computation of the energy of molecules and materials is one of the most promising applications of fault-tolerant quantum computers. Practical applications require development of quantum algorithms with reduced resource requirements. Previous work has mainly focused on quantum algorithms where the Hamiltonian is represented in second quantization with compact basis sets while existing methods in first quantization are limited to a grid-based basis. In this work, we present a new method to solve the generic ground-state chemistry problem in first quantization using any basis set. We achieve asymptotic speedup in Toffoli count for molecular orbitals, and orders of magnitude improvement using dual plane waves as compared to the second quantization counterparts. In some instances, our approach provides similar or even lower resources compared to previous first quantization plane wave algorithms that, unlike our approach, avoids the loading of the classical data. The developed methodology can be applied to variety of applications, where the matrix elements of a first quantized Hamiltonian lack simple circuit representation.
A central question in quantum many-body physics is estimating the ground energy of a
k-local Hamiltonian system. In this work, we present a spectral technique for certifying a lower bound on the ground energy of a random
n-qubit Hamiltonian system defined as the sum of signed
k-local Pauli operators. In particular, we prove that for any constant
ℓ, there exists an efficiently computable length
nO(ℓ) certificate that is always a lower bound on the ground energy with the promise that, with high probability over the random Hamiltonian distribution, the certificate value is an
ε-good approximation of the true ground energy when the number of terms is sufficiently large. Second, we show by construction that this technique, while successful on average over random Hamiltonian systems, can fail to produce good certificates on worst-case instances. Our spectral technique for producing these certificates comes from extending classical results on
k-XOR refutations to
k-local Pauli Hamiltonians by crafting a quantum variant of the Kikuchi matrix for CSP refutations. To show the limitations of this technique, we prove non-commutative Sum-of-Squares lower bounds for worst-case signed
k-local Pauli operators. More generally, we explore how the non-commutative Sum-of-Squares relaxation can be understood as augmenting the standard Sum-of-Squares relaxation with the commutation relations between the Pauli operators. We instantiate the resulting framework with a modification to prior quantum code-based NLTS Hamiltonians that yields stronger complexity guarantees for the low-energy space; our Hamiltonian family satisfies simultaneously (1)
Ω(logn)-circuit depth lower bounds for all low-energy states, (2) constant-gap NP-hardness to approximate the ground energy, and (3) a constant-gap non-commutative Sum-of-Squares integrality gap up to
Ω(n)-levels.
This paper improves and demonstrates the usefulness of the first quantized plane-wave algorithms for the quantum simulation of electronic structure. We describe our quantum algorithm for first quantized simulation that accurately includes pseudopotentials. We focus on the Goedecker-Tetter-Hutter pseudopotential, and despite its complicated form, we block encode the associated operator without significantly increasing the overall cost of quantum simulation. This is surprising since simulating the nuclear potential is much simpler without pseudopotentials, yet is still the bottleneck. We also generalize prior methods to enable the simulation of materials with non-cubic unit cells, which requires nontrivial modifications. Finally, we combine these techniques to estimate block-encoding costs for commercially relevant instances of heterogeneous catalysis (e.g. carbon monoxide adsorption) and compare to the quantum resources needed to simulate materials in second quantization. We conclude that for computational cells with many particles, first quantization often requires meaningfully less spacetime volume.
High Resolution Image Download MS PowerPoint Slide Quantum phase estimation (QPE) is a promising quantum algorithm for obtaining molecular ground-state energies with chemical accuracy. However, its computational cost, dominated by the Hamiltonian 1-norm λ and the cost of the block encoding, scales at least quadratically with the number of molecular orbitals, making it challenging to incorporate dynamic correlation by enlarging the active space. In this work, we investigate two strategies to mitigate this cost through the optimization of the basis set. First, we investigate whether adjusting the coefficients of Gaussian basis functions can minimize the 1-norm while preserving the accuracy of the ground state energy. Although this method leads to a reduction in the 1-norm up to 10%, this reduction is system-dependent and diminishes with increasing molecular size. Second, we demonstrate that employing a large-basis-set frozen natural orbital (FNO) strategy results in a substantial reduction in QPE resources without compromising accuracy. We study a data set of 58 small organic molecules and the dissociation curve of N 2, and demonstrate that an active space constructed from orbitals derived from larger basis sets captures correlation effects more effectively. This approach yields up to an 80% reduction in the 1-norm λ and also leads to a 55% reduction in the number of orbitals. Our results highlight that improving the quality, not just the size, of the orbital basis is a viable strategy for extending QPE to include dynamical correlation, making progress toward scalable and chemically accurate quantum simulations with tractable resource requirements.