AICCM2026DEV-B decisions and open questions¶
Last updated: 2026-06-22.
Decisions¶
ID |
Decision |
Reason |
|---|---|---|
D1 |
Define the method as a finite BvK torus constrained to primitive-translation-invariant RHF determinants. |
Gives a precise Hamiltonian, variational space, and finite-size problem. |
D2 |
Evaluate the cyclic Gamma-supercell problem through the full unreduced Gamma-centred character mesh. |
Exact finite-group Fourier equivalence; reuses the validated SCF/integral infrastructure. |
D3 |
Use Wigner–Seitz weights only to partition tied minimum-image representatives of one translation class. |
Weights sum to one and preserve one- and two-electron permutation symmetries. |
D4 |
Reject the historical pair-product four-centre weighting. |
Its displayed factors are not generally invariant under bra–ket interchange, so a conventional RHF scalar functional does not follow. |
D5 |
In 3D use the common neutral periodic Ewald/GDF gauge, remove the Hartree (G=0) mode, and apply the BvK-supercell exchange Madelung correction. |
Keeps electron–electron, electron–nuclear, nucleus–nucleus, and exchange finite-size conventions consistent in the 3D route. |
D6 |
Reject charged cells and smearing in Phase 1. |
Both require a different explicitly stated variational functional/background convention. |
D7 |
Keep the existing CCM untouched and expose |
Allows head-to-head comparison with no behaviour change to the peer implementation. |
D8 |
Reuse native GDF, Ewald, basis, lattice, canonical orthogonalisation, DIIS, and output infrastructure. |
These are not AICCM-specific; duplicating them would reduce comparability and correctness. |
D9 |
Accept only the pair-resolved RSGDF or MDF fit; reject the q-only |
The latter is not a consistent four-centre finite-torus Hamiltonian on tight cells and has known non-physical fixed points. |
D10 |
Initialise the existing periodic citation flag for non- |
The repo-wide gate exposed an unrelated unbound local in citation output. The false default restores the intended existing behaviour and does not alter any SCF result. |
D11 |
Refresh two stale k-point recommender assertions found by the repo-wide gate. |
They still expected the retired ungated-model error and Fermi–Dirac default, while the shipped implementation and changelog specify the environment gate and Methfessel–Paxton default. Production behaviour is unchanged. |
D12 |
Expose three independently selectable integral backends: |
They allow direct-versus-three-centre consistency tests when their dimensional Coulomb gauges are matched. |
D13 |
Reuse the corrected-gauge BIPOLE Fock engine for |
The former contains direct four-centre short-range J/K plus the complete reciprocal long-range and BvK exchange correction. The legacy path is documented upstream as missing the exchange correction. |
D14 |
Permit closed-shell RHF/RKS in 1D, 2D, and 3D, including hybrids. |
The finite group is dimension independent. The 1D/2D four-center direct-truncated gauge and RI fitted metric are explicitly documented as unmatched absolute-energy conventions. |
D15 |
Fail closed for RI/RIJCOSX RKS and RIJCOSX RHF at a one-cell mesh. |
The native Gamma-only RKS GDF path is not pair-resolved and the COSX bridge is multi-k only; silently falling back would mislabel the backend. |
D16 |
Audit the 2008 deMon2k KS-ADFT CCM separately from the 2014 four-center formula. |
Janetzko et al. use multiplicative occurrence weights, but their Eq. (20) explicitly averages both AO-center orderings. The same bra–ket diagnosis cannot be copied without checking that symmetrization; quotient-space adjoint consistency and long-range truncation remain open. |
D17 |
Transpose the repository’s row-lattice array when constructing the mathematical lattice generator. |
The derivation uses lattice vectors as columns, while |
D18 |
Build B-stream MP2 from the B RI-RHF character-mesh reference, not the existing toroidal Gamma-supercell HF helper. |
The two references differ by 4.6408868 mHa per cell on the two-cell 8 x 12 x 12 bohr H2 control, so substituting the latter changes the finite zeroth-order Hamiltonian. |
D19 |
Use a truncated metric inverse square root expressed in the original auxiliary-AO basis for post-HF momentum blocks. |
Compact eigenspace factors have arbitrary phases and rotations independently at (q) and (-q). The canonical matrix function removes that gauge from cross-block MP2 contractions. |
D20 |
Expose canonical RI-MP2 initially for 3D neutral closed-shell systems and fail closed for 1D/2D. |
The 3D two-point H2 result agrees with external KRHF/KMP2 below one nanohartree per cell. The lower-dimensional long-range convention remains O1 and cannot yet support a single reference Hamiltonian. |
D21 |
Transform the pair-resolved RI Hamiltonian to a real finite torus before local correlation. |
The derived (N_c^{-2}) inverse transform reproduces the momentum-space RI integral normalization exactly and preserves the B reference instead of substituting the legacy Gamma-supercell Hamiltonian. |
D22 |
Count every occupied pair and ordered triples contribution on the finite torus, then divide the total correlation energy by (N_c). |
This is unambiguous and passes the exact-limit oracle. Translation-reduced pair/triple orbits require an orbit-stabilizer derivation and are not approximated by occurrence weights. |
D23 |
Use PBC-safe Pipek–Mezey occupied localization; reject molecular Foster–Boys localization. |
Mulliken populations do not require the ordinary position operator, which is discontinuous on the torus boundary. |
D24 |
Keep pair-distance screening, finite occupied-coupling radii, and local fitting disabled in the B local-correlation route. |
The existing molecular algorithms use Euclidean distances. Minimum-image Wannier and auxiliary domains are required before those approximations can preserve translation symmetry. PNO truncation itself remains available. |
D25 |
Localize one complete finite-torus occupied space, never independent k blocks. |
A single unitary rotation preserves the occupied projector, density, and SCF energy exactly and produces translationally related occupied orbitals for local correlation. |
D26 |
Label the present periodic spread as a projected circular AO-centre approximation, not an exact Marzari–Vanderbilt spread. |
Exact continuum localization needs cross-k exponential-position matrix elements that the integral API does not yet expose. |
D27 |
Construct B-specific PAOs with the metric projector and canonical Gram orthogonalization, and construct PNOs from a Hermitian positive-semidefinite pair density. |
The algebra removes occupied leakage and PAO redundancy and gives nested PNO ranks as the occupation threshold is tightened. MP2 energy errors are not variational and need numerical validation. |
D28 |
Enumerate occupied-pair orbits by closure under measured localization translation permutations, but do not skip representative pairs yet. |
Orbit multiplicities are exact only after translation covariance is proven. The current Wannier control passes, while finite-supercell IAO cross overlaps leave a residual near (10^{-5}). Representative-only amplitude scattering has no energy-parity gate yet. |
D29 |
Expose space-group symmetry as an off-by-default diagnostic and fail closed for integral reduction. |
The compatible finite-cluster subgroup, nonsymmorphic atom/cell maps, irreducible k orbits, and primitive shell-pair/quartet orbit partitions are derived. General-k AO sewing matrices and representative scatter are not yet proven in every backend convention. |
D30 |
Before the real local solver, construct and verify a full-rank real time-reversal gauge; at the complete-domain, zero-PNO-threshold MP2 limit, audit the result with an independent rotation-invariant full-space DF-MP2 contraction. |
The first integration exposed unsafe complex-to-real casts in a solver whose equations are real. Explicit realification preserves the occupied projector. The public result reports both the raw value and any full-space correction. No correction is applied to truncated calculations. |
D31 |
Make the real-space lattice extension the primary user parameter and derive the full Gamma-centered character net from it. |
The method is a finite BvK torus, not two independently converged real- and reciprocal-space approximations. A shell radius (s_i) means (N_i=2s_i+1); the old mesh tuple remains only an exact compatibility alias. |
D32 |
Extend UHF and UKS with independent alpha and beta idempotent projectors on the same finite Hamiltonian. |
Spin changes the variational ranks and exchange contractions, not the translation quotient or Wigner–Seitz partition. Separate density, electron-count, and spin-contamination audits make this explicit. |
D33 |
Build unrestricted post-HF from the exact real transform of the B RI-UHF Hamiltonian. |
Reusing a molecular or legacy Gamma reference would change the finite zeroth-order Hamiltonian. The supercell multiplicity is (N_c(M-1)+1), preserving the spin difference in every primitive cell. |
D34 |
Treat the present unrestricted DLPNO-UCCSD(T) engine as an O(N^6) correctness oracle. |
Full-domain projection proves the PNO exact limit, but translation-representative amplitude propagation and minimum-image domains are not implemented. Calling it production reduced scaling would be false. |
D35 |
Expose only gauge-invariant SCF properties derivable from the finite-net one-particle density. |
Electron/spin counts, Mulliken populations, finite-net gaps, idempotency, and ⟨S²⟩ are defined. Cell dipoles, Berry-phase polarization, analytic response, and correlated properties need additional theory and fail closed. |
Source disagreements recorded¶
The 2014 paper’s numerical convergence is evidence, not a proof of a variational energy. The independent formulation supplies the missing finite Hamiltonian and constrained variational statement.
The historical two-, three-, and four-centre pair-product boundary factors are not adopted.
aiccm2026dev-bweights translation equivalence classes, not arbitrary centre pairs.A converged, plausible energy is not accepted if the density is non-idempotent, the electron count is wrong, the Fock is non-Hermitian, or the finite-mesh/supercell identity fails.
A long-range correction added only to the final scalar energy is insufficient. Its functional derivative must be present in the SCF Fock.
The deMon2k two-center claim that the reference center is arbitrary requires equality of the two weighted representative sums, not only symmetry of the underlying free-space integral. Its explicitly symmetrized three-center Eq. (20), however, already addresses the simplest AO-pair interchange.
Open questions and queued work¶
ID |
Question / work |
Current position |
|---|---|---|
O1 |
One common long-range convention for 1D chains and 2D slabs. |
The B stream now runs all backends in 1D/2D. Four-center uses the direct-truncated lower-dimensional BIPOLE gauge; RI uses its fitted dimensional metric. Their large absolute-energy differences are not fitting errors until a common wire/slab Green function is implemented. |
O2 |
Global-minimum and stability analysis. |
RHF SCF gives a stationary determinant in the constrained space. Add orbital-Hessian/stability checks before production status. |
O3 |
Finite-size convergence law for exact exchange. |
Measure rather than assume monotonicity; fit insulating test ladders by geometry and basis. |
O4 |
Open-shell production validation. |
UHF/UKS now run through four-center, RI, and RIJCOSX in 1D/2D/3D, and 3D UMP2/UCCSD(T)/PNO pilots use the exact B transform. Add external periodic open-shell references, stability analysis, and larger spin-contaminated controls. |
O5 |
KS-DFT production validation. |
Closed-shell RKS now runs through direct, RI, and RIJCOSX backends. Grid convergence, nonlocal functionals, forces, and the historical DFT weighting comparison remain open. |
O6 |
Coupled cluster and local correlation. |
Restricted and unrestricted real-torus PNO MP2/CCSD/(T) routes are implemented in 3D, including full-domain exact-limit oracles. They still evaluate all pairs/triples with full contractions. Translation-representative amplitude propagation, minimum-image screening/local fitting, relaxed correlated densities, and external periodic CC benchmarks remain open. |
O7 |
ECP electron/background bookkeeping. |
Phase 1 is validated first with all-electron minimal bases. Add explicit effective-charge neutrality checks before ECP benchmarks. |
O8 |
3D ionic benchmark ladder. |
LiH, MgO, NaCl, and diamond need matched all-electron basis/reference conventions and full mesh convergence data. |
O9 |
H4 four-centre versus RI discrepancy. |
At the two-cell, 40-bohr-vacuum H4 geometry, corrected-gauge four-centre RHF is -2.1870080428 Ha/cell while RI is -2.1648043358 Ha/cell, a -22.204 mHa difference. The compact H2 two-cell control agrees across all three backends within 44 microhartree. Treat the H4 difference as unresolved truncation/cell-embedding behaviour, not as evidence that either number is the dense-limit oracle. |
O10 |
Exact periodic IAO cross overlap. |
The current IAO target/reference overlap is evaluated in the explicit supercell and omits cross-boundary images. Periodize it before using IAO translations to reduce correlated pairs. |
O11 |
Space-group integral acceleration. |
Derive backend-specific general-k sewing matrices, real-solid-harmonic shell actions, quartet stabilizers, and petite-list scatter. Enable only after symmetry-on/off Fock and energy parity. Layer and rod groups and little-group irrep labels are also open. |
Current measured evidence¶
The committed benchmark was run on the alternating H4/STO-3G chain with a
40-bohr transverse simulation lattice. For cyclic lengths 1, 2, and 4, the
new energy per cell was respectively -2.0733777009, -2.1648043358, and
-2.1719609271 Ha. A direct call to the full Gamma-centred character mesh was
identical to all printed digits at every length. The historical union12
CCM gave -2.1615967328, -2.1618792916, and -2.1707034746 Ha/cell. The
separately developed symmetric aiccm2026dev-a weighting gave the same displayed
sequence in this 1D case. This is useful comparison evidence, not a
correctness proof. New-route wall times in the archived current-main run were
22.58, 20.61, and 97.23 seconds; the four-cell jump reflects all-k-pair
exact-exchange fitting.
That H4 ladder used the ri backend. The backend-crossing smoke benchmark
uses H2/STO-3G in an 8 x 12 x 12 bohr cell at a (2,1,1) cyclic mesh. RHF
energies are -1.1213506456 (four_center), -1.1213722182 (ri), and
-1.1213943367 Ha/cell (rijcosx). PBE0 energies are -1.1554208287,
-1.1554589526, and -1.1554644822 Ha/cell in the same order. These are actual
runs from 2026-06-21; the maximum spread is 43.7 microhartree for RHF and
43.7 microhartree for PBE0. They establish executable cross-backend
consistency on this compact control, not a universal error bound.
The 1D/2D route matrix was also run on H2/STO-3G at a (2,1,1) cyclic mesh. Every RHF and PBE calculation converged through four-center, RI, and RIJCOSX, with idempotency errors below 3e-15. The 1D RHF energies were -1.5341898653, -2.2845855922, and -2.2846076938 Ha/cell; the 2D values were -3.4506478026, -5.2158679833, and -5.2158905993 Ha/cell. The large four-center/RI gaps are the evidence behind O1, not a backend-accuracy result.
The first 3D canonical RI-MP2 control uses an H2/STO-3G cell of
20 x 20 x 6 bohr and the (1,1,2) character mesh. B gives HF, correlation,
and total energies of -1.1182352381008094, -0.0130227001540294, and
-1.1312579382548390 Ha per cell. The out-of-process PySCF 2.13.1
KRHF/KMP2 reference gives -1.1182352386944080, -0.0130226999202183, and
-1.1312579386146264 Ha per cell. The corresponding absolute differences
are below 0.6 nanohartree. The archived record is
docs/manuscripts/aiccm_comparison/data/h2_mp2_2026-06-21.json.
The exact inverse transform was tested by running the existing local solvers
on the real finite torus. H2/STO-3G at the same (1,1,2) mesh gives a
no-truncation local-MP2 correlation energy identical to canonical B RI-MP2
within 7e-18 Ha per cell. A LiH/STO-3G cell of 20 x 20 x 7 bohr at the same
mesh gives canonical finite-torus DF-CCSD and (T) totals of
-0.0302475329439885 and -0.0000934031163267 Ha. The no-truncation local
solver differs by 6.9e-12 and 1.4e-12 Ha, respectively. The nonzero-triples
record and inverse-transform residuals are archived in
docs/manuscripts/aiccm_comparison/data/lih_dlpno_ccsdt_2026-06-21.json.
This is an internal finite-Hamiltonian oracle, not an external
infinite-crystal CCSD(T) result.
The first unrestricted transform control is a neutral Li doublet in a 15 x 15 x 15 bohr cell with STO-3G and extension (1,1,1), run on 2026-06-22. RI-UHF is -7.32670108299121 Ha/cell, UMP2 correlation is -0.000243259672659 Ha/cell, and full-domain UCCSD correlation is -0.000257809105931 Ha/cell. The triples correction is numerically zero for this three-electron minimal-basis control. The transformed RI factor has a 2.31e-16 maximum imaginary residual and a 7.11e-15 permutation residual. Independent alpha/beta localization changes the density by 4.3e-34, and the zero-threshold localized UCCSD(T) total agrees with the canonical gauge within 5e-14 Ha. These values establish the finite-torus unrestricted transform and PNO exact limit only; a one-cell Li array is not a converged crystal benchmark.