Source code for vibeqc.periodic_uhf_multi_k_ewald

"""Phase 15b: multi-k periodic UHF SCF driver using the composed
EWALD_3D Coulomb dispatch.

Open-shell counterpart of :mod:`vibeqc.periodic_rhf_multi_k_ewald`.
Carries two density matrices ``D_α(g), D_β(g)`` per real-space cell
and constructs the per-spin 2e Fock at every k via the composed
Ewald split

    F^{2e,σ}(g)  =  J(D_total, ω)(g)  −  K(D_σ)(g)

with ``D_total = D_α + D_β`` (one-particle convention, no factor 2)
and full-range exchange. The Ewald J is split into a short-range
real-space ``J_SR`` and a long-range FFT-Poisson ``J_LR`` exactly
as in the closed-shell multi-k Fock builder; per-spin K is extracted
from the closed-shell builder via

    K(D_σ)  =  2 · (J_full(D_σ)  −  F_full(D_σ))

where ``J_full(D)`` and ``F_full(D) = J_full(D) − ½ K(D)`` are two
separate ``build_fock_2e_real_space`` calls at ω = 0. Total cost per
iteration: 6 lattice-ERI builds (1 J_SR(D_total) + 1 J_LR(D_total)
+ 2 J_full(D_σ) + 2 F_full(D_σ)) + one FFT Poisson, vs 3 + 1 for
closed-shell multi-k RHF.

Bloch-sums each per-spin F^{2e,σ}(g) to F^{2e,σ}(k), adds Hcore(k),
diagonalises per spin per k. DIIS is per-spin (separate Pulay history
α vs β). Inverse-Bloch fold rebuilds D_α_real and D_β_real from the
per-k MOs each iteration.

Scope
-----

  - Multi-k periodic UHF with EWALD_3D. The Γ-only path (single
    [1,1,1] mesh) reproduces :func:`run_uhf_periodic_gamma_ewald3d`
    by construction (the multi-k builder reduces to the molecular-
    limit J convention at [1,1,1] mesh — same caveat as the RHF
    case).
  - Closed-shell case (multiplicity = 1) reproduces the multi-k
    Ewald RHF energy to ~µHa.
  - Standard HF (no DFT, no smearing). Smearing wired into multi-k
    UHF lands with Phase 15c periodic UKS where it's the more
    common use case.
"""

from __future__ import annotations

import math
from dataclasses import dataclass, field
from typing import List, Optional, Sequence, Tuple, Union

import numpy as np

from ._vibeqc_core import (
    BasisSet,
    BlochKMesh,
    CoulombMethod,
    LatticeMatrixSet,
    LatticeSumOptions,
    PeriodicRHFOptions,
    PeriodicSystem,
    SCFIteration,
    bloch_sum,
    build_fock_2e_real_space,
    compute_kinetic_lattice,
    compute_nuclear_lattice,
    compute_overlap_lattice,
    nuclear_repulsion_per_cell,
    real_space_density_from_kpoints,
    real_space_density_from_kpoints_fractional,
)
from .ewald_j import auto_grid
from .madelung import (
    madelung_energy_correction_for_lat as _madelung_energy_correction_for_lat,
)
from .periodic_density import build_j_long_range_periodic
from .periodic_rhf_multi_k_ewald import (
    _canonical_orthogonalizer_complex,
    _damp_lattice_matrix,
    _diag_in_orth_basis,
    _g0_block,
)
from .periodic_scf_accelerators import (
    DynamicDamping,
    MultiKPeriodicUHFAccelerator,
)
from .periodic_uhf_ewald import _spin_squared
from .progress import ProgressLogger, resolve_progress
from .scf_divergence import check_scf_divergence
from .smearing._support import reject_unsupported_smearing_temperature

__all__ = [
    "PeriodicUHFMultiKEwaldResult",
    "run_uhf_periodic_multi_k_ewald3d",
]


[docs] @dataclass class PeriodicUHFMultiKEwaldResult: """Result of :func:`run_uhf_periodic_multi_k_ewald3d`. Per-cell quantities (``energy``, ``e_electronic``, ``e_nuclear``) plus per-k matrices for each spin (``mo_energies_alpha``, ``mo_coeffs_alpha``, ``fock_alpha``, ``mo_energies_beta``, ...) and the converged real-space densities ``density_alpha``, ``density_beta`` (each a :class:`LatticeMatrixSet`). Reports ``s_squared`` evaluated at the home-cell (Γ-block) MOs. """ energy: float e_electronic: float e_nuclear: float n_iter: int converged: bool s_squared: float s_squared_ideal: float # α spin mo_energies_alpha: List[np.ndarray] mo_coeffs_alpha: List[np.ndarray] fock_alpha: List[np.ndarray] density_alpha: LatticeMatrixSet # β spin mo_energies_beta: List[np.ndarray] mo_coeffs_beta: List[np.ndarray] fock_beta: List[np.ndarray] density_beta: LatticeMatrixSet # Per-k overlap + Hcore (shared between α/β). overlap: List[np.ndarray] hcore: List[np.ndarray] scf_trace: List[SCFIteration] = field(default_factory=list) omega: float = 0.0 grid_shape: Tuple[int, int, int] = (0, 0, 0)
def _build_uhf_fock_blocks_ewald3d( basis: BasisSet, system: PeriodicSystem, D_alpha_real: LatticeMatrixSet, D_beta_real: LatticeMatrixSet, omega: float, lat_opts: LatticeSumOptions, grid_shape_t: Tuple[int, int, int], origin: Optional[Sequence[float]], spacing_bohr: float, ) -> Tuple[List[np.ndarray], List[np.ndarray]]: """Compute per-cell ``(F^{2e,α}(g), F^{2e,β}(g))`` blocks. Six lattice-ERI calls per invocation: - J_SR(D_total, ω): real-space short-range Hartree. - J_LR(D_total, ω): FFT Poisson long-range Hartree. - J_full(D_α): full-range Hartree of D_α (for K extraction). - F_full(D_α): J_full(D_α) − ½ K_full(D_α). - J_full(D_β): same for β. - F_full(D_β): same for β. Then ``K(D_σ) = 2 · (J_full(D_σ) − F_full(D_σ))`` and F^{2e,σ}(g) = J_SR_total(g) + J_LR_total(g) − K(D_σ)(g). """ n_cells = len(D_alpha_real.cells) # Total density D_total = D_α + D_β. Build via the overlap template # and mutate the C++ storage in place via ``set_block``. D_total_real = compute_overlap_lattice(basis, system, lat_opts) for g in range(n_cells): D_total_real.set_block( g, np.asarray(D_alpha_real.blocks[g], dtype=float) + np.asarray(D_beta_real.blocks[g], dtype=float), ) # J(D_total, ω) — Ewald split. J_SR_total_lms = build_fock_2e_real_space( basis, system, lat_opts, D_total_real, 0.0, float(omega), ) J_LR_total_blocks = build_j_long_range_periodic( basis, system, D_total_real, omega=float(omega), grid_shape=grid_shape_t, origin=origin, spacing_bohr=spacing_bohr, output_cells=list(range(n_cells)), ) # Per-spin J_full(D_σ) and F_full(D_σ) at ω = 0. J_full_alpha = build_fock_2e_real_space( basis, system, lat_opts, D_alpha_real, 0.0, 0.0, ) F_full_alpha = build_fock_2e_real_space( basis, system, lat_opts, D_alpha_real, 1.0, 0.0, ) J_full_beta = build_fock_2e_real_space( basis, system, lat_opts, D_beta_real, 0.0, 0.0, ) F_full_beta = build_fock_2e_real_space( basis, system, lat_opts, D_beta_real, 1.0, 0.0, ) F_alpha_blocks: List[np.ndarray] = [] F_beta_blocks: List[np.ndarray] = [] for g in range(n_cells): J_SR_total = np.asarray(J_SR_total_lms.blocks[g], dtype=float) J_LR_total = np.asarray(J_LR_total_blocks[g], dtype=float) J_total = J_SR_total + J_LR_total # K(D_σ) = 2 · (J_full(D_σ) − F_full(D_σ)) since # F_full(D) = J_full(D) − ½ K(D) ⇒ K(D) = 2(J_full − F_full). J_full_a = np.asarray(J_full_alpha.blocks[g], dtype=float) F_full_a = np.asarray(F_full_alpha.blocks[g], dtype=float) K_a = 2.0 * (J_full_a - F_full_a) J_full_b = np.asarray(J_full_beta.blocks[g], dtype=float) F_full_b = np.asarray(F_full_beta.blocks[g], dtype=float) K_b = 2.0 * (J_full_b - F_full_b) F_alpha_blocks.append(J_total - K_a) F_beta_blocks.append(J_total - K_b) return F_alpha_blocks, F_beta_blocks def _bloch_sum_blocks( blocks: Sequence[np.ndarray], cells, k_cart: np.ndarray, ) -> np.ndarray: """F(k) = Σ_g e^{i k·R_g} F(g).""" k = np.asarray(k_cart, dtype=float).reshape(3) F_k = np.zeros_like(blocks[0], dtype=complex) for g_idx, block in enumerate(blocks): R_g = np.asarray(cells[g_idx].r_cart, dtype=float) phase = np.exp(1j * float(np.dot(k, R_g))) F_k = F_k + phase * block return F_k
[docs] def run_uhf_periodic_multi_k_ewald3d( system: PeriodicSystem, basis: BasisSet, kmesh: BlochKMesh, options=None, *, omega: float = 0.0, grid_shape: Optional[Union[Tuple[int, int, int], int]] = None, origin: Optional[Sequence[float]] = None, spacing_bohr: float = 0.3, linear_dep_threshold: float = 1e-7, canonical_orth_normalize_diag_first: bool = True, auto_optimize_truncation: bool = True, progress: Union[bool, ProgressLogger, None] = None, verbose: Optional[int] = None, ) -> PeriodicUHFMultiKEwaldResult: """Multi-k open-shell UHF SCF with EWALD_3D Coulomb. Mirror of :func:`run_rhf_periodic_multi_k_ewald3d` for open-shell systems. Same DIIS / damping / orthogonaliser conventions, but everything runs per-spin: two Pulay-DIIS instances, two diagonalisations per k, two density matrices folded back via inverse Bloch. Occupations follow the molecule's multiplicity (assumed equal at every k — closed-shell-insulator-flavoured setup, matching the multi-k RHF driver). """ from ._vibeqc_core import PeriodicRHFOptions as _Opts opts = options if options is not None else _Opts() reject_unsupported_smearing_temperature( opts, "run_uhf_periodic_multi_k_ewald3d", detail=( "UHF needs spin-resolved fractional occupations and chemical " "potentials; use closed-shell RHF/RKS smearing or leave " "smearing_temperature at 0.0." ), ) lat_opts: LatticeSumOptions = opts.lattice_opts plog = resolve_progress(progress, verbose=verbose) # ω must match the nuclear Ewald α (auto-selected from # nuclear_cutoff_bohr in the C++ ewald engine) so that the # jellium background terms cancel exactly — see the matching # block in run_rhf_periodic_gamma_ewald3d. User can override via # opts.ewald_omega (rarely needed). The driver kwarg ``omega`` is # retained for signature parity but is overridden here. _ewald_tol = getattr(opts, "ewald_tolerance", 1e-12) _cutoff = getattr(opts, "ewald_cutoff_bohr", lat_opts.nuclear_cutoff_bohr) if omega <= 0.0: _user_omega = getattr(opts, "ewald_omega", None) if _user_omega is not None and float(_user_omega) > 0.0: omega = float(_user_omega) else: from .bipole_ext_el_pole import crystal_default_ewald_alpha V_cell = float(abs(np.linalg.det(np.asarray(system.lattice, dtype=float)))) omega = crystal_default_ewald_alpha(V_cell) lat = np.asarray(system.lattice, dtype=float) if grid_shape is None: grid_shape_t = auto_grid(lat, spacing_bohr) elif isinstance(grid_shape, int): grid_shape_t = (grid_shape, grid_shape, grid_shape) else: grid_shape_t = tuple(int(x) for x in grid_shape) plog.info( f"UHF multi-k EWALD_3D / omega = {float(omega):.3f}, " f"FFT grid {grid_shape_t[0]}x{grid_shape_t[1]}x{grid_shape_t[2]}" ) plog.info(f"basis: {basis.name} ({basis.nbasis} BFs / {basis.nshells} shells)") from .options_dump import dump_active_settings dump_active_settings( plog, [ ("PeriodicRHFOptions", opts), ("LatticeSumOptions", lat_opts), ( "Driver kwargs", { "omega": float(omega), "grid_shape": grid_shape_t, "origin": origin, "spacing_bohr": float(spacing_bohr), "linear_dep_threshold": float(linear_dep_threshold), "canonical_orth_normalize_diag_first": canonical_orth_normalize_diag_first, "auto_optimize_truncation": auto_optimize_truncation, }, ), ], ) if plog.level >= 5: from .scf_log import format_basis_summary plog.write_raw(format_basis_summary(basis)) # Open-shell occupations. n_elec = int(system.n_electrons()) mult = int(system.multiplicity) if mult < 1: raise ValueError( f"run_uhf_periodic_multi_k_ewald3d: multiplicity must be ≥ 1, got {mult}" ) if (n_elec + mult - 1) % 2 != 0 or (n_elec - mult + 1) % 2 != 0: raise ValueError( f"run_uhf_periodic_multi_k_ewald3d: (n_electrons={n_elec}, " f"multiplicity={mult}) cannot be split into integer α/β." ) n_alpha = (n_elec + mult - 1) // 2 n_beta = (n_elec - mult + 1) // 2 k_points = list(kmesh.kpoints) weights = np.asarray(kmesh.weights, dtype=float) n_k = len(k_points) if n_k == 0: raise ValueError("kmesh has no k-points") if not np.isclose(weights.sum(), 1.0): raise ValueError(f"kmesh.weights must sum to 1; got {weights.sum():.6f}") plog.info( f"k-mesh: {n_k} k-point{'s' if n_k != 1 else ''}, " f"weights sum = {weights.sum():.4f}; " f"n_alpha = {n_alpha}, n_beta = {n_beta}" ) # ---- Auto-optimise lattice truncation (default ON) ------------------- if auto_optimize_truncation and lat_opts.coulomb_method == CoulombMethod.EWALD_3D: from .eigs_preflight import ( format_truncation_optimization_report, optimize_truncation, ) k_arr = [np.asarray(k, dtype=float) for k in k_points] opt_rep = optimize_truncation( system, basis, lattice_opts=lat_opts, k_points_cart=k_arr, ) if ( opt_rep.n_evaluations > 1 or opt_rep.optimized_lattice_opts.cutoff_bohr != lat_opts.cutoff_bohr ): plog.write_raw(format_truncation_optimization_report(opt_rep)) if not opt_rep.converged: plog.warning("auto_optimize_truncation did not converge.") lat_opts = opt_rep.optimized_lattice_opts # ---- Real-space one-electron integrals ------------------------------- with plog.stage( "integrals_lattice", detail=f"S/T/V at cutoff {lat_opts.cutoff_bohr:.2f} bohr" ): S_lat = compute_overlap_lattice(basis, system, lat_opts) T_lat = compute_kinetic_lattice(basis, system, lat_opts) from .periodic_v_ne import compute_nuclear_lattice_dispatch V_lat = compute_nuclear_lattice_dispatch(basis, system, lat_opts) cells = list(S_lat.cells) n_cells = len(cells) # Per-k S(k), Hcore(k), orthogonaliser X(k). S_k_list: List[np.ndarray] = [] Hcore_k_list: List[np.ndarray] = [] X_k_list: List[np.ndarray] = [] # Per-k linear-dependence preflight; see periodic_rhf_multi_k_ewald # for the rationale (Searle et al., ARCHER eCSE04-16, 2017). from .linear_dependence import scf_preflight_overlap_check for k_idx, k in enumerate(k_points): k_arr = np.asarray(k, dtype=float).reshape(3) S_k = np.asarray(bloch_sum(S_lat, k_arr)) T_k = np.asarray(bloch_sum(T_lat, k_arr)) V_k = np.asarray(bloch_sum(V_lat, k_arr)) H_k = T_k + V_k S_k = 0.5 * (S_k + S_k.conj().T) H_k = 0.5 * (H_k + H_k.conj().T) scf_preflight_overlap_check( S_k, plog=plog, label=f"S(k={k_idx}, k_cart={k_arr.round(4).tolist()})", basis=basis, ) X_k, n_kept = _canonical_orthogonalizer_complex( S_k, linear_dep_threshold, normalize_diag_first=canonical_orth_normalize_diag_first, ) if max(n_alpha, n_beta) > n_kept: raise RuntimeError( f"run_uhf_periodic_multi_k_ewald3d: orth dropped too many " f"directions (n_α={n_alpha}, n_β={n_beta}, " f"n_kept={n_kept}) at k = {k_arr}" ) S_k_list.append(S_k) Hcore_k_list.append(H_k) X_k_list.append(X_k) e_nuc = float(nuclear_repulsion_per_cell(system, lat_opts)) # ---- Initial guess: diagonalize Hcore(k) for both spins. C_alpha_per_k: List[np.ndarray] = [] eps_alpha_per_k: List[np.ndarray] = [] C_beta_per_k: List[np.ndarray] = [] eps_beta_per_k: List[np.ndarray] = [] for H_k, X_k in zip(Hcore_k_list, X_k_list): C_a, eps_a = _diag_in_orth_basis(H_k, X_k) C_b, eps_b = _diag_in_orth_basis(H_k, X_k) C_alpha_per_k.append(C_a.astype(complex)) eps_alpha_per_k.append(eps_a) C_beta_per_k.append(C_b.astype(complex)) eps_beta_per_k.append(eps_b) # Build initial real-space densities. UHF densities are per-spin # one-particle (no factor 2). Use the fractional-occupation C++ # density builder with occupations of 1.0 (rather than 2.0) to # build the spin density directly — sidesteps the # LatticeMatrixSet.blocks-is-a-Python-list-copy mutation footgun # the closed-shell-then-halve approach hit on first try. def _spin_density(C_per_k_local, n_occ_each): """Build a one-particle (no factor 2) real-space spin density via the C++ fractional-occupation builder.""" nbf = C_per_k_local[0].shape[1] occ_per_k = [] for _ in range(n_k): occ = np.zeros(nbf, dtype=float) occ[:n_occ_each] = 1.0 occ_per_k.append(occ) return real_space_density_from_kpoints_fractional( C_per_k_local, occ_per_k, kmesh, cells, ) D_alpha_real = _spin_density(C_alpha_per_k, n_alpha) D_beta_real = _spin_density(C_beta_per_k, n_beta) D_alpha_prev: Optional[LatticeMatrixSet] = None D_beta_prev: Optional[LatticeMatrixSet] = None damping = float(opts.damping) if not (0.0 <= damping < 1.0): raise ValueError( f"run_uhf_periodic_multi_k_ewald3d: damping must be in " f"[0, 1); got {damping}" ) use_diis = bool(opts.use_diis) diis_start_iter = int(opts.diis_start_iter) accel: Optional[MultiKPeriodicUHFAccelerator] = ( MultiKPeriodicUHFAccelerator(opts) if use_diis else None ) damper: Optional[DynamicDamping] = None if bool(getattr(opts, "dynamic_damping", False)): damper = DynamicDamping( initial_alpha=damping, alpha_min=float(getattr(opts, "dynamic_damping_min", 0.0)), alpha_max=float(getattr(opts, "dynamic_damping_max", 0.95)), ) level_shift = float(getattr(opts, "level_shift", 0.0)) # Phase C1c — quadratic SCF fallback (per-spin per-k Newton step). quadratic_fallback_iter = int(getattr(opts, "quadratic_fallback_iter", 0)) quadratic_fallback_shift = float(getattr(opts, "quadratic_fallback_shift", 0.1)) quadratic_fallback_max_step = float( getattr(opts, "quadratic_fallback_max_step", 0.1) ) # ---- SCF loop -------------------------------------------------------- plog.banner("SCF (UHF multi-k, EWALD_3D)") plog.info(" iter energy (Ha) dE ||[F,DS]|| DIIS") scf_trace: List[SCFIteration] = [] E_prev = 0.0 F_alpha_k_list: List[np.ndarray] = [np.zeros_like(H) for H in Hcore_k_list] F_beta_k_list: List[np.ndarray] = [np.zeros_like(H) for H in Hcore_k_list] converged = False iter_idx = 0 for iter_idx in range(1, int(opts.max_iter) + 1): if damper is not None: damping = damper.alpha diis_active = use_diis and iter_idx >= diis_start_iter # Density damping (per-spin) when DIIS not yet active. if iter_idx > 1 and damping > 0.0 and not diis_active: D_alpha_used = _damp_lattice_matrix( D_alpha_real, D_alpha_prev, damping, ) D_beta_used = _damp_lattice_matrix( D_beta_real, D_beta_prev, damping, ) else: D_alpha_used = D_alpha_real D_beta_used = D_beta_real # 2e Fock blocks for both spins. F_alpha_blocks, F_beta_blocks = _build_uhf_fock_blocks_ewald3d( basis, system, D_alpha_used, D_beta_used, omega, lat_opts, grid_shape_t, origin, spacing_bohr, ) # Bloch-sum to per-k F^{2e,σ}(k) and add Hcore(k). F_alpha_k_list = [] F_beta_k_list = [] for k_idx, k_cart in enumerate(k_points): F_a = _bloch_sum_blocks(F_alpha_blocks, cells, np.asarray(k_cart)) F_b = _bloch_sum_blocks(F_beta_blocks, cells, np.asarray(k_cart)) F_a = F_a + Hcore_k_list[k_idx] F_b = F_b + Hcore_k_list[k_idx] F_alpha_k_list.append(F_a) F_beta_k_list.append(F_b) # Per-cell electronic energy + per-k commutator errors. # E_elec = ½ tr[D_total · Hcore] + ½ tr[D_α · F_α] + ½ tr[D_β · F_β] E_elec = 0.0 grad_norm_sum = 0.0 error_alpha_k_list: List[np.ndarray] = [] error_beta_k_list: List[np.ndarray] = [] for idx in range(n_k): C_a = C_alpha_per_k[idx] C_b = C_beta_per_k[idx] C_a_occ = C_a[:, :n_alpha] if n_alpha > 0 else C_a[:, :0] C_b_occ = C_b[:, :n_beta] if n_beta > 0 else C_b[:, :0] D_a_k = C_a_occ @ C_a_occ.conj().T D_b_k = C_b_occ @ C_b_occ.conj().T H_k = Hcore_k_list[idx] F_a_k = F_alpha_k_list[idx] F_b_k = F_beta_k_list[idx] w = float(weights[idx]) E_elec += w * ( 0.5 * np.real(np.trace((D_a_k + D_b_k) @ H_k)) + 0.5 * np.real(np.trace(D_a_k @ F_a_k)) + 0.5 * np.real(np.trace(D_b_k @ F_b_k)) ) S_k = S_k_list[idx] FDS_a = F_a_k @ D_a_k @ S_k FDS_b = F_b_k @ D_b_k @ S_k err_a = FDS_a - FDS_a.conj().T err_b = FDS_b - FDS_b.conj().T error_alpha_k_list.append(err_a) error_beta_k_list.append(err_b) grad_norm_sum += w * float( np.sqrt(np.linalg.norm(err_a) ** 2 + np.linalg.norm(err_b) ** 2) ) # Madelung-leak correction (v0.6.1). _D_g0 = np.asarray(_g0_block(D_alpha_real)) + np.asarray(_g0_block(D_beta_real)) _S_g0 = np.asarray(_g0_block(S_lat)) E_madelung_fix = _madelung_energy_correction_for_lat( _D_g0, _S_g0, system, lat_opts ) E_total = float(E_elec) + e_nuc + E_madelung_fix dE = E_total - E_prev # Divergence detection (v0.6.2). check_scf_divergence( "run_uhf_periodic_multi_k_ewald3d", iter_idx, E_total, grad_norm_sum, dE, ) diis_sub = accel.subspace_size if accel is not None else 0 scf_trace.append( SCFIteration( iter=iter_idx, energy=float(E_total), delta_e=float(dE if iter_idx > 1 else 0.0), grad_norm=float(grad_norm_sum), diis_subspace=diis_sub, ) ) plog.iteration( iter_idx, energy=float(E_total), dE=float(dE if iter_idx > 1 else 0.0), grad=float(grad_norm_sum), diis=diis_sub, ) converged = ( iter_idx > 1 and abs(dE) < float(opts.conv_tol_energy) and grad_norm_sum < float(opts.conv_tol_grad) ) # Phase C1c gate. When the quadratic fallback is active, take # per-spin per-k Newton steps in MO space — bypass DIIS and # level shift since the Newton step is its own update. in_quadratic_phase = ( quadratic_fallback_iter > 0 and iter_idx > quadratic_fallback_iter ) new_C_alpha: List[np.ndarray] = [] new_eps_alpha: List[np.ndarray] = [] new_C_beta: List[np.ndarray] = [] new_eps_beta: List[np.ndarray] = [] if in_quadratic_phase: from .quadratic_scf import quadratic_step for idx in range(n_k): C_a, eps_a = quadratic_step( F_alpha_k_list[idx], C_alpha_per_k[idx], eps_alpha_per_k[idx], n_alpha, shift=quadratic_fallback_shift, max_step=quadratic_fallback_max_step, ) C_b, eps_b = quadratic_step( F_beta_k_list[idx], C_beta_per_k[idx], eps_beta_per_k[idx], n_beta, shift=quadratic_fallback_shift, max_step=quadratic_fallback_max_step, ) new_C_alpha.append(C_a) new_eps_alpha.append(eps_a) new_C_beta.append(C_b) new_eps_beta.append(eps_b) else: # SCF-accelerator extrapolation. DIIS runs per-spin # per-k Pulay internally; KDIIS / EDIIS / ADIIS use a # single spin-coupled history (one coefficient set # applied to both spins). For the bridged paths # (EDIIS / ADIIS / EDIIS_DIIS) we Bloch-sum the per-cell # D_α / D_β densities to per-k for input. if accel is not None: density_alpha_k_list = [ _bloch_sum_blocks( D_alpha_used.blocks, D_alpha_used.cells, np.asarray(k), ) for k in k_points ] density_beta_k_list = [ _bloch_sum_blocks( D_beta_used.blocks, D_beta_used.cells, np.asarray(k), ) for k in k_points ] F_a_ex, F_b_ex = accel.extrapolate_uhf( F_alpha_k_list, F_beta_k_list, error_alpha_k_list=error_alpha_k_list, error_beta_k_list=error_beta_k_list, density_alpha_k_list=density_alpha_k_list, density_beta_k_list=density_beta_k_list, energy=E_total, mo_coeffs_alpha_k_list=C_alpha_per_k, mo_coeffs_beta_k_list=C_beta_per_k, n_alpha=n_alpha, n_beta=n_beta, weights=list(weights), cells=cells, kpoints=list(k_points), ) if diis_active: F_alpha_k_list = F_a_ex F_beta_k_list = F_b_ex # Optional Saunders-Hillier level shift per spin per k. if level_shift != 0.0: for idx in range(n_k): S_k = S_k_list[idx] C_a = C_alpha_per_k[idx] C_b = C_beta_per_k[idx] C_a_occ = C_a[:, :n_alpha] if n_alpha > 0 else C_a[:, :0] C_b_occ = C_b[:, :n_beta] if n_beta > 0 else C_b[:, :0] # UHF densities are 1·C_occ·C_occ† (no factor 2). D_a_k = C_a_occ @ C_a_occ.conj().T D_b_k = C_b_occ @ C_b_occ.conj().T F_alpha_k_list[idx] = ( F_alpha_k_list[idx] + level_shift * S_k - level_shift * (S_k @ D_a_k @ S_k) ) F_beta_k_list[idx] = ( F_beta_k_list[idx] + level_shift * S_k - level_shift * (S_k @ D_b_k @ S_k) ) F_alpha_k_list[idx] = 0.5 * ( F_alpha_k_list[idx] + F_alpha_k_list[idx].conj().T ) F_beta_k_list[idx] = 0.5 * ( F_beta_k_list[idx] + F_beta_k_list[idx].conj().T ) for idx in range(n_k): C_a, eps_a = _diag_in_orth_basis( F_alpha_k_list[idx], X_k_list[idx], ) C_b, eps_b = _diag_in_orth_basis( F_beta_k_list[idx], X_k_list[idx], ) new_C_alpha.append(C_a) new_eps_alpha.append(eps_a) new_C_beta.append(C_b) new_eps_beta.append(eps_b) C_alpha_per_k = new_C_alpha eps_alpha_per_k = new_eps_alpha C_beta_per_k = new_C_beta eps_beta_per_k = new_eps_beta # Rebuild D_α, D_β real-space densities (one-particle conv). D_alpha_new = _spin_density(C_alpha_per_k, n_alpha) D_beta_new = _spin_density(C_beta_per_k, n_beta) D_alpha_prev = D_alpha_used D_beta_prev = D_beta_used D_alpha_real = D_alpha_new D_beta_real = D_beta_new if damper is not None: damper.update(E_total) E_prev = E_total if converged: break # ---- Final pass on converged D's -------------------------------------- if converged: F_alpha_blocks, F_beta_blocks = _build_uhf_fock_blocks_ewald3d( basis, system, D_alpha_real, D_beta_real, omega, lat_opts, grid_shape_t, origin, spacing_bohr, ) F_alpha_k_list = [] F_beta_k_list = [] E_elec = 0.0 for k_idx, k_cart in enumerate(k_points): F_a = _bloch_sum_blocks(F_alpha_blocks, cells, np.asarray(k_cart)) F_b = _bloch_sum_blocks(F_beta_blocks, cells, np.asarray(k_cart)) F_a = F_a + Hcore_k_list[k_idx] F_b = F_b + Hcore_k_list[k_idx] F_alpha_k_list.append(F_a) F_beta_k_list.append(F_b) final_C_alpha: List[np.ndarray] = [] final_C_beta: List[np.ndarray] = [] final_eps_alpha: List[np.ndarray] = [] final_eps_beta: List[np.ndarray] = [] for idx in range(n_k): C_a, eps_a = _diag_in_orth_basis( F_alpha_k_list[idx], X_k_list[idx], ) C_b, eps_b = _diag_in_orth_basis( F_beta_k_list[idx], X_k_list[idx], ) final_C_alpha.append(C_a) final_C_beta.append(C_b) final_eps_alpha.append(eps_a) final_eps_beta.append(eps_b) C_a_occ = C_a[:, :n_alpha] if n_alpha > 0 else C_a[:, :0] C_b_occ = C_b[:, :n_beta] if n_beta > 0 else C_b[:, :0] D_a_k = C_a_occ @ C_a_occ.conj().T D_b_k = C_b_occ @ C_b_occ.conj().T w = float(weights[idx]) E_elec += w * ( 0.5 * np.real(np.trace((D_a_k + D_b_k) @ Hcore_k_list[idx])) + 0.5 * np.real(np.trace(D_a_k @ F_alpha_k_list[idx])) + 0.5 * np.real(np.trace(D_b_k @ F_beta_k_list[idx])) ) C_alpha_per_k = final_C_alpha C_beta_per_k = final_C_beta eps_alpha_per_k = final_eps_alpha eps_beta_per_k = final_eps_beta # Madelung-leak correction (v0.6.1). _D_g0_f = np.asarray(_g0_block(D_alpha_real)) + np.asarray( _g0_block(D_beta_real) ) _S_g0_f = np.asarray(_g0_block(S_lat)) E_madelung_fix_f = _madelung_energy_correction_for_lat( _D_g0_f, _S_g0_f, system, lat_opts ) E_total = float(E_elec) + e_nuc + E_madelung_fix_f # ⟨S²⟩ from the home-cell (Γ-block) MOs as a representative # diagnostic. Multi-k ⟨S²⟩ is more involved; this is the standard # quick check used by PySCF.pbc / CRYSTAL. if n_alpha == 0 or n_beta == 0: s2 = 0.25 * (n_alpha - n_beta) * (n_alpha - n_beta + 2) + n_beta else: # Use k=0 if present, else first k. k0_idx = 0 for i, k in enumerate(k_points): if np.allclose(np.asarray(k), 0.0): k0_idx = i break S_real = np.real(S_k_list[k0_idx]) s2 = _spin_squared( n_alpha, n_beta, np.real(C_alpha_per_k[k0_idx]), np.real(C_beta_per_k[k0_idx]), S_real, ) plog.converged(n_iter=iter_idx, energy=E_total, converged=converged) return PeriodicUHFMultiKEwaldResult( energy=E_total, e_electronic=float(E_elec), e_nuclear=e_nuc, n_iter=iter_idx, converged=converged, s_squared=float(s2), s_squared_ideal=0.25 * (mult - 1) * (mult + 1), mo_energies_alpha=eps_alpha_per_k, mo_coeffs_alpha=C_alpha_per_k, fock_alpha=F_alpha_k_list, density_alpha=D_alpha_real, mo_energies_beta=eps_beta_per_k, mo_coeffs_beta=C_beta_per_k, fock_beta=F_beta_k_list, density_beta=D_beta_real, overlap=S_k_list, hcore=Hcore_k_list, scf_trace=scf_trace, omega=float(omega), grid_shape=grid_shape_t, )