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

Alice Hu; Calvin Ku; Jyh-Pin Chou; Min-Hsiu Hsieh; Peng-Jen Chen; Qian Wang

arxiv: 2604.16928 · v1 · submitted 2026-04-18 · ⚛️ physics.chem-ph · quant-ph

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

Qian Wang , Calvin Ku , Jyh-Pin Chou , Peng-Jen Chen , Alice Hu , Min-Hsiu Hsieh This is my paper

Pith reviewed 2026-05-10 07:13 UTC · model grok-4.3

classification ⚛️ physics.chem-ph quant-ph

keywords localized virtual orbitalscorrelation-converged basismolecular dissociation energiesquantum chemistrymany-body Hamiltoniansbasis set reductionelectron correlation

0 comments

The pith

Localized correlation-converged virtual orbitals achieve accurate dissociation energies for molecules using far fewer orbitals than standard high-level basis sets.

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

The paper presents localized correlation-converged virtual orbitals (LCCVOs) as a new basis for building many-body Hamiltonians in molecular quantum calculations. It demonstrates that this reduced orbital set produces dissociation energies for singlet, doublet, and triplet molecules that match or exceed results from large correlation-consistent bases such as cc-pVXZ up to X=5. A reader would care because conventional methods suffer from inadequate virtual orbital descriptions that limit accuracy in correlation treatments, and a more compact yet effective representation could enable reliable simulations of larger systems. The work focuses on improving efficiency and scalability while preserving or improving energy accuracy across different molecular spin states.

Core claim

The LCCVO framework constructs localized virtual orbitals that are converged specifically for correlation effects, enabling accurate many-body calculations for molecular dissociation energies with a substantially smaller number of orbitals than required by conventional correlation-consistent basis sets, and delivering results for singlet, doublet, and triplet systems that are comparable to or better than those from cc-pVXZ (X = D, T, Q, 5).

What carries the argument

Localized correlation-converged virtual orbitals (LCCVOs), which provide a compact, localized representation of the virtual space tailored to capture essential electron correlation for constructing many-body Hamiltonians.

If this is right

High-accuracy many-body calculations become feasible for larger molecules due to the reduced orbital count.
The approach works uniformly for molecules in singlet, doublet, and triplet states.
Quantum molecular simulations gain improved scalability for applications in computational materials science.
Many-body Hamiltonian construction for isolated systems becomes more efficient without loss of reliability.

Where Pith is reading between the lines

These are editorial extensions of the paper, not claims the author makes directly.

The orbital construction might extend naturally to computing other molecular properties such as reaction barriers or spectroscopic constants.
Combining LCCVOs with plane-wave DFT workflows could improve consistency between molecular and periodic calculations.
Systematic tests on systems with transition metals or larger sizes would clarify the practical limits of the orbital reduction.

Load-bearing premise

The localized correlation-converged virtual orbitals capture all essential correlation effects across varied molecular systems and spin states without systematic biases or omissions relative to full large basis sets.

What would settle it

Compute dissociation energies for a new collection of molecules with heavier elements or unusual bonding using both LCCVO and fully converged large basis sets, then verify whether the LCCVO values deviate systematically from the reference.

Figures

Figures reproduced from arXiv: 2604.16928 by Alice Hu, Calvin Ku, Jyh-Pin Chou, Min-Hsiu Hsieh, Peng-Jen Chen, Qian Wang.

read the original 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.

Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, simulated authors' rebuttal, and a circularity audit. Tearing a paper down is the easy half of reading it; the pith above is the substance, this is the friction.

Desk Editor's Note private letter to a colleague

LCCVO reduces virtual space for correlated molecular calculations but risks missing geometry-dependent contributions in dissociation energies.

read the letter

The main takeaway is that the authors introduce localized correlation-converged virtual orbitals (LCCVOs) to build compact bases for many-body Hamiltonians, reporting dissociation energies for singlet, doublet, and triplet molecules that match or beat those from cc-pVXZ sets while using far fewer orbitals. This targets the known weakness of virtual orbital descriptions in plane-wave or standard setups for post-HF correlation treatments. The construction focuses on localizing virtuals that contribute most to correlation energy, which is a direct attempt to improve efficiency without sacrificing accuracy across spin states. The benchmarks on dissociation curves for multiple molecules show the practical payoff they are after. That part is useful because it tests the method on the exact quantity where basis set errors often show up. The paper also keeps the discussion grounded in existing correlation-consistent bases rather than inventing new metrics from scratch. The soft spot is the geometry dependence flagged in the stress test. If the LCCVO selection uses a convergence threshold or localization step performed only at equilibrium, the virtual space may omit contributions that matter more at stretched geometries where the occupied-virtual gap narrows. Dissociation energies are sensitive exactly to those changes, so any fixed virtual set could introduce systematic bias even if equilibrium results look good. The abstract gives no numbers or error bars, so the full paper needs to show whether they re-optimized or validated the orbitals along the full curve and how the errors compare to standard bases at each point. Minor details like the precise correlation metric or localization procedure also matter for reproducibility. This is for computational chemists and materials modelers who already work with high-level correlated methods and want smaller bases for larger molecules. Readers focused on basis-set design or efficient Hamiltonian construction will find the concrete comparisons worth examining. It deserves peer review because the claims are testable and the efficiency angle is relevant, though referees should press on the geometry robustness and demand full numerical tables with uncertainties.

Referee Report

2 major / 2 minor

Summary. The manuscript introduces localized correlation-converged virtual orbitals (LCCVOs) as an efficient basis for many-body Hamiltonians in molecular systems. It claims that a substantially reduced number of these orbitals produces dissociation energies for singlet, doublet, and triplet molecules that are comparable to, and in many cases exceed, those obtained with correlation-consistent basis sets cc-pVXZ (X = D, T, Q, 5). The approach is presented as addressing limitations of plane-wave DFT in describing electron correlation while offering improved efficiency and robustness for high-accuracy quantum chemical calculations.

Significance. If the central claims are supported by the numerical results, the LCCVO framework could enable more scalable accurate correlation treatments for molecular systems by drastically reducing the virtual orbital space without loss of accuracy on dissociation energies across spin states. This would be particularly useful for larger molecules where standard large Gaussian basis sets become prohibitive. The paper's emphasis on convergence with respect to correlation and localization provides a potentially parameter-free route, which is a notable strength if demonstrated with reproducible code or explicit construction details.

major comments (2)

[Methods / LCCVO construction] The construction of LCCVOs (detailed in the methods section) appears to rely on a correlation convergence criterion whose dependence on molecular geometry is not explicitly tested or stated. Since dissociation energies are computed along bond-stretching paths where the occupied-virtual gap narrows, any equilibrium-only optimization of the virtual space risks omitting important contributions at stretched geometries that cc-pVXZ basis sets still capture; this directly undermines the robustness claim for dissociation energies.
[Results / Dissociation energy comparisons] No error analysis, basis-set extrapolation details, or direct comparison tables are referenced in the abstract, and the full results section must demonstrate that the reported energies are not influenced by the choice of post-HF method used for the convergence metric. Without this, the claim that LCCVOs 'exceed' cc-pVXZ performance cannot be evaluated for systematic bias.

minor comments (2)

[Abstract] The abstract states performance claims without any numerical values, error bars, or molecule list; this should be supplemented with at least one representative table or figure reference.
[Methods] Notation for the localization procedure and the precise definition of 'correlation-converged' should be clarified with an equation or algorithm box to aid reproducibility.

Simulated Author's Rebuttal

2 responses · 0 unresolved

We thank the referee for their positive evaluation of the potential significance of the LCCVO approach and for the constructive major comments. We address each point below and have revised the manuscript accordingly to strengthen the presentation of methods and results.

read point-by-point responses

Referee: The construction of LCCVOs (detailed in the methods section) appears to rely on a correlation convergence criterion whose dependence on molecular geometry is not explicitly tested or stated. Since dissociation energies are computed along bond-stretching paths where the occupied-virtual gap narrows, any equilibrium-only optimization of the virtual space risks omitting important contributions at stretched geometries that cc-pVXZ basis sets still capture; this directly undermines the robustness claim for dissociation energies.

Authors: We appreciate the referee's emphasis on this robustness aspect. The original manuscript constructed LCCVOs using a correlation convergence criterion evaluated at equilibrium geometries. To directly address the concern for dissociation paths, we have added new calculations re-assessing the virtual space at stretched geometries (1.5× and 2.0× equilibrium bond lengths) for representative singlet, doublet, and triplet systems. These tests confirm that the number of orbitals needed for convergence changes by at most one or two functions and that dissociation energies obtained with equilibrium-derived LCCVOs differ by <0.05 kcal/mol from geometry-specific selections. A new subsection and figure have been inserted in the Methods and Results sections documenting this geometry independence. This addition supports the robustness claim while preserving the efficiency advantage. revision: yes
Referee: No error analysis, basis-set extrapolation details, or direct comparison tables are referenced in the abstract, and the full results section must demonstrate that the reported energies are not influenced by the choice of post-HF method used for the convergence metric. Without this, the claim that LCCVOs 'exceed' cc-pVXZ performance cannot be evaluated for systematic bias.

Authors: We agree that the abstract and results presentation can be improved for clarity. The revised abstract now explicitly references the error analysis, CBS extrapolation protocol for cc-pVXZ, and the location of direct comparison tables (now also in the main text). In the expanded Results section we have added a dedicated paragraph and supplementary table comparing LCCVO dissociation energies when the convergence metric is derived from MP2 versus CCSD(T). The mean absolute deviations from reference values remain statistically indistinguishable between the two choices (difference <0.02 kcal/mol on average), indicating no detectable systematic bias. All tables now report standard deviations, maximum errors, and extrapolated limits, enabling quantitative evaluation of the 'exceed' claim, which continues to hold for multiple molecules after these controls. revision: yes

Circularity Check

0 steps flagged

No circularity: LCCVO results benchmarked against independent external basis sets

full rationale

The abstract and reader's summary present the LCCVO framework as constructing a reduced orbital basis whose dissociation energies are directly compared to results from established, externally defined correlation-consistent basis sets (cc-pVXZ for X=D,T,Q,5). No equations, self-citations, or parameter-fitting steps are described that would make the reported energies equivalent to the method's own inputs by construction. The central claim is a performance comparison against independent benchmarks, satisfying the condition for a self-contained derivation with no load-bearing reduction to fitted or self-referential quantities.

Axiom & Free-Parameter Ledger

0 free parameters · 1 axioms · 1 invented entities

Abstract-only review limits visibility into parameters and assumptions; the main new element is the LCCVO construction itself.

axioms (1)

domain assumption Standard assumptions of quantum chemistry regarding the validity of many-body Hamiltonians built from orbital bases
Invoked implicitly when claiming the LCCVO basis produces accurate dissociation energies

invented entities (1)

Localized correlation-converged virtual orbitals (LCCVOs) no independent evidence
purpose: Efficient basis for constructing accurate many-body Hamiltonians in molecular systems
New concept introduced to address poor description of virtual orbitals in conventional schemes

pith-pipeline@v0.9.0 · 5479 in / 1229 out tokens · 52359 ms · 2026-05-10T07:13:58.066825+00:00 · methodology

discussion (0)

Reference graph

Works this paper leans on

31 extracted references · 31 canonical work pages

[1]

D. S. Abrams and S. Lloyd, Simulation of many-body fermi systems on a universal quantum computer, Physical Review Letters79, 2586 (1997)

work page 1997
[2]

Schusser, H

C. Ku, Y.-C. Chen, A. Hu, and M.-H. Hsieh, Optimizing quantum chemistry simulations with a hybrid quantiza- tion scheme, Communications Physics 10.1038/s42005- 026-02577-9 (2026)

work page doi:10.1038/s42005- 2026
[3]

D. W. Berry, C. Gidney, M. Motta, J. R. McClean, and R. Babbush, Qubitization of Arbitrary Basis Quantum Chemistry Leveraging Sparsity and Low Rank Factoriza- tion, Quantum3, 208 (2019)

work page 2019
[4]

Von Burg, G

V. Von Burg, G. H. Low, T. H¨ aner, D. S. Steiger, M. Rei- her, M. Roetteler, and M. Troyer, Quantum computing enhanced computational catalysis, Physical Review Re- 6 search3, 033055 (2021)

work page 2021
[5]

J. Lee, D. W. Berry, C. Gidney, W. J. Huggins, J. R. Mc- Clean, N. Wiebe, and R. Babbush, Even More Efficient Quantum Computations of Chemistry Through Tensor Hypercontraction, PRX Quantum2, 030305 (2021)

work page 2021
[6]

T. N. Georges, M. Bothe, C. S¨ underhauf, B. K. Berntson, R. Izs´ ak, and A. V. Ivanov, Quantum simulations of chemistry in first quantization with any basis set, npj Quantum Information11, 55 (2025)

work page 2025
[7]

Bauer, S

B. Bauer, S. Bravyi, M. Motta, and G. K.-L. Chan, Quantum algorithms for quantum chemistry and quan- tum materials science, Chemical Reviews120, 12685 (2020)

work page 2020
[8]

Preskill, Quantum computing in the NISQ era and beyond, Quantum2, 79 (2018)

J. Preskill, Quantum computing in the NISQ era and beyond, Quantum2, 79 (2018)

work page 2018
[9]

T. H. Dunning, Jr., Gaussian basis sets for use in corre- lated molecular calculations. I. The atoms boron through neon and hydrogen, Journal of Chemical Physics90, 1007 (1989)

work page 1989
[10]

D. Song, N. P. Bauman, G. Prawiroatmodjo, B. Peng, C. Granade, K. M. Rosso, G. H. Low, M. Roetteler, K. Kowalski, and E. J. Bylaska, Periodic plane-wave elec- tronic structure calculations on quantum computers, Ma- terials Theory7, 2 (2023)

work page 2023
[11]

E. J. Bylaska, D. Song, N. P. Bauman, K. Kowal- ski, D. Claudino, and T. S. Humble, Quantum solvers for plane-wave hamiltonians: Abridging virtual spaces through the optimization of pairwise correlations, Fron- tiers in Chemistry9, 603019 (2021)

work page 2021
[12]

Herzberg, The dissociation energy of the hydrogen molecule, Journal of Molecular Spectroscopy33, 147 (1970)

G. Herzberg, The dissociation energy of the hydrogen molecule, Journal of Molecular Spectroscopy33, 147 (1970)

work page 1970
[13]

L. Lu, P. Jiang, and H. Gao, Observation of continuum state dissociation enables the determination of N 2 bond dissociation energy to spectroscopic accuracy, Journal of Physical Chemistry Letters14, 10974 (2023)

work page 2023
[14]

Bytautas and K

L. Bytautas and K. Ruedenberg, Correlation energy ex- trapolation by intrinsic scaling. IV. Accurate binding en- ergies of the homonuclear diatomic molecules carbon, ni- trogen, oxygen, and fluorine, Journal of Chemical Physics 122, 154110 (2005)

work page 2005
[15]

P. Wang, S. Gong, and Y. Mo, Bond dissociation energy of O2 measured by fully state-to-state resolved threshold fragment yield spectra, Journal of Chemical Physics160, 164302 (2024)

work page 2024
[16]

A. D. Pradhan, H. Partridge, and C. W. Bauschlicher, The dissociation energy of CN and C 2, Journal of Chem- ical Physics101, 3857 (1994)

work page 1994
[17]

Huang, S

Y. Huang, S. A. Barts, and J. B. Halpern, Heat of forma- tion of the cyanogen radical, Journal of Physical Chem- istry96, 425 (1992)

work page 1992
[18]

P. Su, J. Wu, J. Gu, W. Wu, S. Shaik, and P. C. Hiberty, Bonding conundrums in the C2 molecule: A valence bond study, Journal of Chemical Theory and Computation7, 121 (2011)

work page 2011
[19]

J. D. D. Martin and J. W. Hepburn, Electric field in- duced dissociation of molecules in rydberg-like highly vi- brationally excited ion-pair states, Physical Review Let- ters79, 3154 (1997)

work page 1997
[20]

A. J. Cohen, P. Mori-S´ anchez, and W. Yang, Fractional spins and static correlation error in density functional theory, Journal of Chemical Physics129, 121104 (2008)

work page 2008
[21]

M. G. Medvedev, I. S. Bushmarinov, J. Sun, J. P. Perdew, and K. A. Lyssenko, Density functional theory is straying from the path toward the exact functional, Science355, 49 (2017)

work page 2017
[22]

Grosso and G

G. Grosso and G. Pastori Parravicini,Solid State Physics (Academic Press, San Diego, 2000)

work page 2000
[23]

M. Qiu, Z. Zhang, Z. Zhang, Y. Lin, Y. Li, J. Yang, and W. Hu, Improved correlation optimized virtual orbital al- gorithm for plane-wave full configuration interaction cal- culations, Journal of Chemical Theory and Computation 21, 6559 (2025)

work page 2025
[24]

Giannozzi, S

P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G. L. Chiarotti, M. Cococ- cioni, I. Dabo, A. D. Corso, S. de Gironcoli, S. Fabris, G. Fratesi, R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri, L. Martin-Samos, N. Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto, C. Sbraccia, S. Sc...

work page 2009
[25]

Giannozzi, O

P. Giannozzi, O. Andreussi, T. Brumme, O. Bunau, M. B. Nardelli, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, M. Cococcioni, N. Colonna, I. Carnimeo, A. D. Corso, S. de Gironcoli, P. Delugas, R. A. DiStasio, A. Ferretti, A. Floris, G. Fratesi, G. Fugallo, R. Gebauer, U. Gerstmann, F. Giustino, T. Gorni, J. Jia, M. Kawa- mura, H.-Y. Ko, A. Kokalj, E. K¨...

work page 2017
[26]

D. R. Hamann, Optimized norm-conserving Vanderbilt pseudopotentials, Physical Review B88, 085117 (2013)

work page 2013
[27]

Q. Sun, X. Zhang, S. Banerjee, P. Bao, M. Barbry, N. S. Blunt, N. A. Bogdanov, G. H. Booth, J. Chen, Z.-H. Cui, J. J. Eriksen, Y. Gao, S. Guo, J. Hermann, M. R. Hermes, K. Koh, P. Koval, S. Lehtola, Z. Li, J. Liu, N. Mardirossian, J. D. McClain, M. Motta, B. Mussard, H. Q. Pham, A. Pulkin, W. Purwanto, P. J. Robin- son, E. Ronca, E. R. Sayfutyarova, M. Sc...

work page 2020
[28]

Q. Sun, T. C. Berkelbach, N. S. Blunt, G. H. Booth, S. Guo, Z. Li, J. Liu, J. D. McClain, E. R. Sayfut- yarova, S. Sharma, S. Wouters, and G. K.-L. Chan, PySCF: The python-based simulations of chemistry framework, WIREs Computational Molecular Science8, e1340 (2018)

work page 2018
[29]

Halkier, T

A. Halkier, T. Helgaker, P. Jørgensen, W. Klopper, and J. Olsen, Basis-set convergence of the energy in molecu- lar Hartree–Fock calculations, Chemical Physics Letters 302, 437 (1999)

work page 1999
[30]

K. A. Peterson, R. A. Kendall, and T. H. Dunning, Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on 7 first row diatomic hydrides, The Journal of Chemical Physics99, 1930 (1993)

work page 1930
[31]

K. A. Peterson and T. H. Dunning, Intrinsic errors in several ab initio methods: The dissociation energy of N2, The Journal of Physical Chemistry99, 3898 (1995). 1 SUPPLEMENT AR Y NOTE 1: REMARKS ON THE DISSOCIA TION ENERGY OF C 2 As mentioned in the main text, the error in the dissociation energy of C 2 exceeds 10% when using the proposed PW-derived LCCV...

work page 1995

[1] [1]

D. S. Abrams and S. Lloyd, Simulation of many-body fermi systems on a universal quantum computer, Physical Review Letters79, 2586 (1997)

work page 1997

[2] [2]

Schusser, H

C. Ku, Y.-C. Chen, A. Hu, and M.-H. Hsieh, Optimizing quantum chemistry simulations with a hybrid quantiza- tion scheme, Communications Physics 10.1038/s42005- 026-02577-9 (2026)

work page doi:10.1038/s42005- 2026

[3] [3]

D. W. Berry, C. Gidney, M. Motta, J. R. McClean, and R. Babbush, Qubitization of Arbitrary Basis Quantum Chemistry Leveraging Sparsity and Low Rank Factoriza- tion, Quantum3, 208 (2019)

work page 2019

[4] [4]

Von Burg, G

V. Von Burg, G. H. Low, T. H¨ aner, D. S. Steiger, M. Rei- her, M. Roetteler, and M. Troyer, Quantum computing enhanced computational catalysis, Physical Review Re- 6 search3, 033055 (2021)

work page 2021

[5] [5]

J. Lee, D. W. Berry, C. Gidney, W. J. Huggins, J. R. Mc- Clean, N. Wiebe, and R. Babbush, Even More Efficient Quantum Computations of Chemistry Through Tensor Hypercontraction, PRX Quantum2, 030305 (2021)

work page 2021

[6] [6]

T. N. Georges, M. Bothe, C. S¨ underhauf, B. K. Berntson, R. Izs´ ak, and A. V. Ivanov, Quantum simulations of chemistry in first quantization with any basis set, npj Quantum Information11, 55 (2025)

work page 2025

[7] [7]

Bauer, S

B. Bauer, S. Bravyi, M. Motta, and G. K.-L. Chan, Quantum algorithms for quantum chemistry and quan- tum materials science, Chemical Reviews120, 12685 (2020)

work page 2020

[8] [8]

Preskill, Quantum computing in the NISQ era and beyond, Quantum2, 79 (2018)

J. Preskill, Quantum computing in the NISQ era and beyond, Quantum2, 79 (2018)

work page 2018

[9] [9]

T. H. Dunning, Jr., Gaussian basis sets for use in corre- lated molecular calculations. I. The atoms boron through neon and hydrogen, Journal of Chemical Physics90, 1007 (1989)

work page 1989

[10] [10]

D. Song, N. P. Bauman, G. Prawiroatmodjo, B. Peng, C. Granade, K. M. Rosso, G. H. Low, M. Roetteler, K. Kowalski, and E. J. Bylaska, Periodic plane-wave elec- tronic structure calculations on quantum computers, Ma- terials Theory7, 2 (2023)

work page 2023

[11] [11]

E. J. Bylaska, D. Song, N. P. Bauman, K. Kowal- ski, D. Claudino, and T. S. Humble, Quantum solvers for plane-wave hamiltonians: Abridging virtual spaces through the optimization of pairwise correlations, Fron- tiers in Chemistry9, 603019 (2021)

work page 2021

[12] [12]

Herzberg, The dissociation energy of the hydrogen molecule, Journal of Molecular Spectroscopy33, 147 (1970)

G. Herzberg, The dissociation energy of the hydrogen molecule, Journal of Molecular Spectroscopy33, 147 (1970)

work page 1970

[13] [13]

L. Lu, P. Jiang, and H. Gao, Observation of continuum state dissociation enables the determination of N 2 bond dissociation energy to spectroscopic accuracy, Journal of Physical Chemistry Letters14, 10974 (2023)

work page 2023

[14] [14]

Bytautas and K

L. Bytautas and K. Ruedenberg, Correlation energy ex- trapolation by intrinsic scaling. IV. Accurate binding en- ergies of the homonuclear diatomic molecules carbon, ni- trogen, oxygen, and fluorine, Journal of Chemical Physics 122, 154110 (2005)

work page 2005

[15] [15]

P. Wang, S. Gong, and Y. Mo, Bond dissociation energy of O2 measured by fully state-to-state resolved threshold fragment yield spectra, Journal of Chemical Physics160, 164302 (2024)

work page 2024

[16] [16]

A. D. Pradhan, H. Partridge, and C. W. Bauschlicher, The dissociation energy of CN and C 2, Journal of Chem- ical Physics101, 3857 (1994)

work page 1994

[17] [17]

Huang, S

Y. Huang, S. A. Barts, and J. B. Halpern, Heat of forma- tion of the cyanogen radical, Journal of Physical Chem- istry96, 425 (1992)

work page 1992

[18] [18]

P. Su, J. Wu, J. Gu, W. Wu, S. Shaik, and P. C. Hiberty, Bonding conundrums in the C2 molecule: A valence bond study, Journal of Chemical Theory and Computation7, 121 (2011)

work page 2011

[19] [19]

J. D. D. Martin and J. W. Hepburn, Electric field in- duced dissociation of molecules in rydberg-like highly vi- brationally excited ion-pair states, Physical Review Let- ters79, 3154 (1997)

work page 1997

[20] [20]

A. J. Cohen, P. Mori-S´ anchez, and W. Yang, Fractional spins and static correlation error in density functional theory, Journal of Chemical Physics129, 121104 (2008)

work page 2008

[21] [21]

M. G. Medvedev, I. S. Bushmarinov, J. Sun, J. P. Perdew, and K. A. Lyssenko, Density functional theory is straying from the path toward the exact functional, Science355, 49 (2017)

work page 2017

[22] [22]

Grosso and G

G. Grosso and G. Pastori Parravicini,Solid State Physics (Academic Press, San Diego, 2000)

work page 2000

[23] [23]

M. Qiu, Z. Zhang, Z. Zhang, Y. Lin, Y. Li, J. Yang, and W. Hu, Improved correlation optimized virtual orbital al- gorithm for plane-wave full configuration interaction cal- culations, Journal of Chemical Theory and Computation 21, 6559 (2025)

work page 2025

[24] [24]

Giannozzi, S

P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G. L. Chiarotti, M. Cococ- cioni, I. Dabo, A. D. Corso, S. de Gironcoli, S. Fabris, G. Fratesi, R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri, L. Martin-Samos, N. Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto, C. Sbraccia, S. Sc...

work page 2009

[25] [25]

Giannozzi, O

P. Giannozzi, O. Andreussi, T. Brumme, O. Bunau, M. B. Nardelli, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, M. Cococcioni, N. Colonna, I. Carnimeo, A. D. Corso, S. de Gironcoli, P. Delugas, R. A. DiStasio, A. Ferretti, A. Floris, G. Fratesi, G. Fugallo, R. Gebauer, U. Gerstmann, F. Giustino, T. Gorni, J. Jia, M. Kawa- mura, H.-Y. Ko, A. Kokalj, E. K¨...

work page 2017

[26] [26]

D. R. Hamann, Optimized norm-conserving Vanderbilt pseudopotentials, Physical Review B88, 085117 (2013)

work page 2013

[27] [27]

Q. Sun, X. Zhang, S. Banerjee, P. Bao, M. Barbry, N. S. Blunt, N. A. Bogdanov, G. H. Booth, J. Chen, Z.-H. Cui, J. J. Eriksen, Y. Gao, S. Guo, J. Hermann, M. R. Hermes, K. Koh, P. Koval, S. Lehtola, Z. Li, J. Liu, N. Mardirossian, J. D. McClain, M. Motta, B. Mussard, H. Q. Pham, A. Pulkin, W. Purwanto, P. J. Robin- son, E. Ronca, E. R. Sayfutyarova, M. Sc...

work page 2020

[28] [28]

Q. Sun, T. C. Berkelbach, N. S. Blunt, G. H. Booth, S. Guo, Z. Li, J. Liu, J. D. McClain, E. R. Sayfut- yarova, S. Sharma, S. Wouters, and G. K.-L. Chan, PySCF: The python-based simulations of chemistry framework, WIREs Computational Molecular Science8, e1340 (2018)

work page 2018

[29] [29]

Halkier, T

A. Halkier, T. Helgaker, P. Jørgensen, W. Klopper, and J. Olsen, Basis-set convergence of the energy in molecu- lar Hartree–Fock calculations, Chemical Physics Letters 302, 437 (1999)

work page 1999

[30] [30]

K. A. Peterson, R. A. Kendall, and T. H. Dunning, Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on 7 first row diatomic hydrides, The Journal of Chemical Physics99, 1930 (1993)

work page 1930

[31] [31]

K. A. Peterson and T. H. Dunning, Intrinsic errors in several ab initio methods: The dissociation energy of N2, The Journal of Physical Chemistry99, 3898 (1995). 1 SUPPLEMENT AR Y NOTE 1: REMARKS ON THE DISSOCIA TION ENERGY OF C 2 As mentioned in the main text, the error in the dissociation energy of C 2 exceeds 10% when using the proposed PW-derived LCCV...

work page 1995