Correlation-Converged Virtual Orbitals for Accurate and Efficient Quantum Molecular Simulations

• URL: http://arxiv.org/abs/2604.16928v1
• Date: Sat, 18 Apr 2026 09:26:16 GMT
• Title: Correlation-Converged Virtual Orbitals for Accurate and Efficient Quantum Molecular Simulations
• Abstract summary: We introduce localized correlation-converged virtual orbitals (LCCVOs) as an efficient basis for constructing accurate many-body Hamiltonians in molecular systems.<n>LCCVOs yield energies for singlet, doublet, and triplet molecules that are comparable to dissociation, and in many cases exceed, those obtained with high-level correlation-consistent basis sets.
• Score: 12.323419069912674
• License: http://arxiv.org/licenses/nonexclusive-distrib/1.0/
• Abstract: Density functional theory with plane-wave basis sets is widely employed in computational materials science, including applications to isolated molecular systems. However, the inadequate description of electron correlation remains a fundamental limitation. Accurate correlation treatments based on many-body Hamiltonians require reliable representations of both occupied and virtual orbitals, yet virtual orbitals are often poorly described in conventional computational schemes, resulting in reduced accuracy. In this work, we introduce localized correlation-converged virtual orbitals (LCCVOs) as an efficient basis for constructing accurate many-body Hamiltonians in molecular systems. Using a substantially reduced number of orbitals, the LCCVO framework yields dissociation energies for singlet, doublet, and triplet molecules that are comparable to, and in many cases exceed, those obtained with high-level correlation-consistent basis sets such as cc-pVXZ (X = D, T, Q, 5). These results demonstrate the efficiency, scalability, and robustness of the LCCVO approach for high-accuracy quantum chemical calculations.

Related papers

• Learning the Kohn-Sham map with neural operators for quasi-linear scaling density functional theory [57.90994363143731]
  Kohn--Sham density functional theory (DFT) underpins electronic-structure simulations.<n>Repeated orbital diagonalizations lead to cubic scaling, restricting quantum calculations to modest scales only.<n>We develop a learning target for orbital-free DFT that maps a Kohn--Sham potential directly to the corresponding density and noninteracting kinetic energy.
  arXiv  Detail & Related papers  (2026-08-24T23:05:42Z)
• Coupled Cluster con MōLe: Molecular Orbital Learning for Neural Wavefunctions [34.53033480184221]
  Density functional theory (DFT) is the most widely used method for calculating molecular properties.<n> Coupled-cluster (CC) theory is the most successful method for achieving accuracy beyond DFT.<n>We present the Molecular Orbital Learning (MLe) architecture, an equivariant machine learning model that directly predicts CC's core mathematical objects.
  arXiv  Detail & Related papers  (2026-02-23T18:54:46Z)
• Elucidating Many-Body Effects in Molecular Core Spectra through Real-Time Approaches: Efficient Classical Approximations and a Quantum Perspective [5.186218508509959]
  We introduce a hierarchy of cost-effective approximate TD-dCC ansatzes derived from truncated Baker-Campbell-Hausdorff (BCH) expansions.<n>We develop a detailed component analysis that isolates hole-mediated excitation pathways, which are correlated processes arising from the coupling between ground-state and ionized-state amplitudes.<n>We demonstrate that the approximate TD-dCC methods closely and efficiently reproduce exact many-body spectral features and quasiparticle weights.
  arXiv  Detail & Related papers  (2025-11-22T08:56:04Z)
• Efficiency of Dynamical Decoupling for (Almost) Any Spin-Boson Model [44.99833362998488]
  We analytically study the dynamical decoupling of a two-level system coupled with a structured bosonic environment.<n>We find sufficient conditions under which dynamical decoupling works for such systems.<n>Our bounds reproduce the correct scaling in various relevant system parameters.
  arXiv  Detail & Related papers  (2024-09-24T04:58:28Z)
• A quantum eigenvalue solver based on tensor networks [0.0]
  Electronic ground states are of central importance in chemical simulations, but have remained beyond the reach of efficient classical algorithms. We introduce a hybrid quantum-classical eigenvalue solver that constructs a wavefunction ansatz from a linear combination of matrix product states in rotated orbital bases. This study suggests a promising new avenue for scaling up simulations of strongly correlated chemical systems on near-term quantum hardware.
  arXiv  Detail & Related papers  (2024-04-16T02:04:47Z)
• Capturing many-body correlation effects with quantum and classical computing [40.7853309684189]
  We show the efficiency of Quantum Phase Estor (QPE) in identifying core-level states relevant to x-ray photoelectron spectroscopy. We compare and validate the QPE predictions with exact diagonalization and real-time equation-of-motion coupled cluster formulations.
  arXiv  Detail & Related papers  (2024-02-18T01:26:45Z)
• Modeling Non-Covalent Interatomic Interactions on a Photonic Quantum Computer [50.24983453990065]
  We show that the cQDO model lends itself naturally to simulation on a photonic quantum computer. We calculate the binding energy curve of diatomic systems by leveraging Xanadu's Strawberry Fields photonics library. Remarkably, we find that two coupled bosonic QDOs exhibit a stable bond.
  arXiv  Detail & Related papers  (2023-06-14T14:44:12Z)
• Calculating non-linear response functions for multi-dimensional electronic spectroscopy using dyadic non-Markovian quantum state diffusion [68.8204255655161]
  We present a methodology for simulating multi-dimensional electronic spectra of molecular aggregates with coupling electronic excitation to a structured environment. A crucial aspect of our approach is that we propagate the NMQSD equation in a doubled system Hilbert space but with the same noise.
  arXiv  Detail & Related papers  (2022-07-06T15:30:38Z)
• Quantum-Classical Hybrid Algorithm for the Simulation of All-Electron Correlation [58.720142291102135]
  We present a novel hybrid-classical algorithm that computes a molecule's all-electron energy and properties on the classical computer. We demonstrate the ability of the quantum-classical hybrid algorithms to achieve chemically relevant results and accuracy on currently available quantum computers.
  arXiv  Detail & Related papers  (2021-06-22T18:00:00Z)
• Quantum Solvers for Plane-Wave Hamiltonians: Abridging Virtual Spaces Through the Optimization of Pairwise Correlations [0.2462953128215087]
  We develop new classes of algorithms to define virtual spaces by optimizing orbitals from small pairwise CI Hamiltonians. Using these derived basis sets for quantum computing calculations targeting full CI (FCI) quality-results can also be used in many-body approaches.
  arXiv  Detail & Related papers  (2020-08-31T19:55:48Z)
• Resource Efficient Chemistry on Quantum Computers with the Variational Quantum Eigensolver and The Double Unitary Coupled-Cluster approach [0.0]
  We show that the number of qubits scales linearly with the size of molecular basis. We employ the double unitary coupled-cluster (DUCC) method to effectively downfold correlation effects into the reduced-size orbital space. Using downfolding techniques, we demonstrate that properly constructed effective Hamiltonians can capture the effect of the whole orbital space in small-size active spaces.
  arXiv  Detail & Related papers  (2020-04-16T15:59:15Z)

This list is automatically generated from the titles and abstracts of the papers in this site.

This site does not guarantee the quality of this site (including all information) and is not responsible for any consequences.