Source code for vibeqc.pbc_bipole_uhf

"""BIPOLE-style periodic UHF driver in CRYSTAL's electrostatic gauge.

This is the open-shell counterpart of :mod:`vibeqc.pbc_bipole`. It keeps
the same CRYSTAL-inspired composition:

* ``V_ne`` and ``E_nn`` share one explicit 3D Ewald state.
* The default 3D two-electron build uses ``J_SR(a) + J_LR(a)`` for the
  Hartree operator with that same alpha, plus full-range per-spin
  exchange from the direct real-space builder.
* Energies are evaluated by real-space lattice contractions so the
  first local SAD/Hcore cycle has the same accounting convention as the
  RHF BIPOLE driver.

The exact Ewald-J route is the production spin-unrestricted energy path.
The Saunders-Dovesi-Roetti far-pair multipole replacement is wired as an
experimental opt-in branch and remains off by default until its
interaction-tensor normalization and end-to-end accuracy are certified.
"""

from __future__ import annotations

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

import numpy as np

from ._vibeqc_core import (
    BasisSet,
    BlochKMesh,
    EwaldOptions,
    GridOptions,
    InitialGuess,
    LatticeMatrixSet,
    LatticeSumOptions,
    PeriodicRHFOptions,
    PeriodicSystem,
    SCFIteration,
    bloch_sum,
    compute_kinetic_lattice,
    compute_overlap_lattice,
    direct_lattice_cells,
    ewald_nuclear_repulsion,
    make_lattice_matrix_set,
    nuclear_repulsion_per_cell,
    real_space_density_from_kpoints_fractional,
)
from .bipole_ext_el_pole import compute_ext_el_spheropole
from .guess import initial_densities_open_shell, initial_density_closed_shell
from .level_shift_schedule import LevelShiftSchedule
from .mom import select_occupied_by_max_overlap as _mom_select
from .oda import compute_oda_lambda as _compute_oda_lambda
from .oda import oda_mix_densities as _oda_mix
from .pbc_bipole_common import (
    PBCBipoleEnergyComponents,
    _bloch_sum_blocks,
    _combine_density_sets,
    _compute_nuclear_lattice_ewald_reciprocal_ft,
    _copy_lattice_with_blocks,
    _crystal_ewald_options,
    _default_bipole_v_ne_grid_options,
    _expand_ibz_kmesh_for_ewald_j,
    _lattice_contract,
    _lattice_contract_blocks,
    _spin_occupations,
    _zero_cross_cell_density,
    bvk_torus_density_matrices,
    prepare_bipole_lattice_options,
    resolve_bipole_fock_symmetry,
    warn_bipole_charged_cell,
    warn_bipole_legacy_multik_gauge,
    home_cell_block,
    smearing_basin_warning,
)
from .pbc_bipole_fock import (
    BipoleFockContext,
    BipoleUnrestrictedFockBuild,
    build_bipole_unrestricted_fock,
)
from .periodic_rhf_multi_k_ewald import (
    _canonical_orthogonalizer_complex,
    _damp_lattice_matrix,
    _diag_in_orth_basis,
)
from .periodic_scf_accelerators import (
    DynamicDamping,
    MultiKPeriodicUHFAccelerator,
)
from .periodic_uhf_ewald import _spin_squared
from .periodic_v_ne import compute_nuclear_lattice_dispatch
from .progress import ProgressLogger, resolve_progress
from .scf_divergence import check_scf_divergence
from .symmetry_integrals_reduced import (
    compute_kinetic_lattice_reduced,
    compute_overlap_lattice_reduced,
)

__all__ = [
    "PBCBipoleUHFResult",
    "run_pbc_bipole_uhf",
]


[docs] @dataclass class PBCBipoleUHFResult: """Result of :func:`run_pbc_bipole_uhf`.""" energy: float e_electronic: float e_nuclear: float n_iter: int converged: bool s_squared: float s_squared_ideal: float mo_energies_alpha: List[np.ndarray] mo_coeffs_alpha: List[np.ndarray] fock_alpha: List[np.ndarray] density_alpha: LatticeMatrixSet mo_energies_beta: List[np.ndarray] mo_coeffs_beta: List[np.ndarray] fock_beta: List[np.ndarray] density_beta: LatticeMatrixSet overlap: List[np.ndarray] hcore: List[np.ndarray] scf_trace: List[SCFIteration] = field(default_factory=list) e_ext_el_spheropole: Optional[float] = None ewald_alpha_bohr_inv: Optional[float] = None # Dudarev DFT+U contribution per unit cell (Hartree). 0 unless # the caller passed ``dft_plus_u=[HubbardSite(...)]``. e_dft_plus_u: float = 0.0 energy_components: List[PBCBipoleEnergyComponents] = field( default_factory=list, ) # Gauge provenance (option (b)): True when the run used the # corrected gauge (full-Bloch density, no spheropole, per-spin # Ewald exchange split). exchange_ewald_split: bool = False exchange_exxdiv: Optional[str] = None # Non-None when finite-T smearing straddled the HOMO-LUMO gap and may # have selected a near-metallic basin (ionic-Gamma basin trap). basin_warning: Optional[str] = None # Smearing diagnostics (zero when smearing_temperature == 0). smearing_temperature: float = 0.0 fermi_level: float = 0.0 entropy: float = 0.0 free_energy: float = 0.0 occupations_alpha: List[np.ndarray] = field(default_factory=list) occupations_beta: List[np.ndarray] = field(default_factory=list) # Cartesian k-points (bohr^-1) and weights this result spans, in the # same order as the per-k, per-spin ``mo_coeffs_*`` / ``mo_energies_*`` # lists. Lets optional single-k output writers locate Gamma instead of # assuming the first k-point is Gamma. See PBCBipoleRHFResult. kpoints_cart: Optional[np.ndarray] = None kpoint_weights: Optional[np.ndarray] = None
[docs] def run_pbc_bipole_uhf( system: PeriodicSystem, basis: BasisSet, kmesh: BlochKMesh, options: Optional[PeriodicRHFOptions] = None, *, linear_dep_threshold: float = 1e-7, canonical_orth_normalize_diag_first: bool = True, level_shift_schedule: Optional[LevelShiftSchedule] = None, use_mom: bool = False, use_oda: bool = False, oda_trust_lambda_max: float = 1.0, use_incremental_fock: bool = True, use_ewald_j_split: Optional[bool] = None, ewald_omega: Optional[float] = None, ewald_precision: float = 1e-8, v_ne_grid_options: Optional[GridOptions] = None, use_multipole_far_field: bool = False, multipole_l_max: int = 2, use_exchange_ewald_split: Optional[bool] = None, exchange_exxdiv: str = "ewald", use_fock_symmetry: Optional[bool] = None, use_fock_symmetry_reduce: bool = False, sr_image_extent_bohr: Optional[float] = None, progress: Union[bool, ProgressLogger, None] = None, verbose: Optional[int] = None, init_alpha: Optional[Sequence[np.ndarray]] = None, init_beta: Optional[Sequence[np.ndarray]] = None, dft_plus_u: Optional[List["HubbardSite"]] = None, ) -> PBCBipoleUHFResult: """Multi-k open-shell UHF via the CRYSTAL-gauge BIPOLE scaffold. ``dft_plus_u``: optional list of :class:`HubbardSite`. When set, the Dudarev +U term is added per-spin per-k after the standard BIPOLE Fock build: * ``n_s^A_l = S_k w_k Re[(S(k) P_s(k) S(k))_{(A,l)}]`` per spin. * ``V_AO_s = U_eff (1/2 - n_s)`` (k-independent). * Per-k Fock contribution: ``F_s(k) += S(k) V_AO_s S(k)``. * Energy: ``E_U_total = S_s (U_eff/2)(tr n_s - tr n_s^2)`` per spin sum, reported via ``result.e_dft_plus_u``. """ opts = options if options is not None else PeriodicRHFOptions() # SPINLOCK. SPIN_SCHEDULE (two-phase) is delegated before SCF setup; # PATTERN_HOLD reuses the per-k MOM machinery below (the same kernel as # use_mom), gated to cycles 2..spinlock_iterations. from .spinlock_periodic import check_spinlock_support, run_spin_schedule from ._vibeqc_core import SpinlockMode if (getattr(opts, "spinlock_mode", SpinlockMode.OFF) == SpinlockMode.SPIN_SCHEDULE and int(getattr(opts, "spinlock_iterations", 0)) > 0): return run_spin_schedule( lambda sysx, o: run_pbc_bipole_uhf( sysx, basis, kmesh, o, linear_dep_threshold=linear_dep_threshold, canonical_orth_normalize_diag_first=canonical_orth_normalize_diag_first, level_shift_schedule=level_shift_schedule, use_mom=use_mom, use_oda=use_oda, oda_trust_lambda_max=oda_trust_lambda_max, use_incremental_fock=use_incremental_fock, use_ewald_j_split=use_ewald_j_split, ewald_omega=ewald_omega, ewald_precision=ewald_precision, v_ne_grid_options=v_ne_grid_options, use_multipole_far_field=use_multipole_far_field, multipole_l_max=multipole_l_max, use_exchange_ewald_split=use_exchange_ewald_split, exchange_exxdiv=exchange_exxdiv, use_fock_symmetry=use_fock_symmetry, use_fock_symmetry_reduce=use_fock_symmetry_reduce, progress=progress, verbose=verbose, dft_plus_u=dft_plus_u, ), system, opts, ) check_spinlock_support( opts, {SpinlockMode.PATTERN_HOLD, SpinlockMode.SPIN_SCHEDULE}, "the BIPOLE UHF driver") smearing_T = float(getattr(opts, "smearing_temperature", 0.0)) if smearing_T < 0.0: raise ValueError("run_pbc_bipole_uhf: smearing_temperature must be >= 0") lat_opts: LatticeSumOptions = opts.lattice_opts plog = resolve_progress(progress, verbose=verbose) ( use_ewald_j_split, use_ewald_j_split_auto, lat_opts_2e, lat_opts_1e, ) = prepare_bipole_lattice_options(system, lat_opts, use_ewald_j_split, plog) n_elec = int(system.n_electrons()) n_alpha, n_beta = _spin_occupations(system) mult = int(system.multiplicity) _kmesh_ibz = kmesh _ir_mapping = np.asarray(getattr(kmesh, "ir_mapping", []), dtype=int).reshape(-1) k_points = list(_kmesh_ibz.kpoints) weights = np.asarray(_kmesh_ibz.weights, dtype=float) if use_ewald_j_split and _ir_mapping.size > 0: # IBZ inputs run on the EXPANDED full mesh (correctness: the # IBZ-native replication shortcut lacked the star AO rotations # D(R.k) = P(R).D(k).P(R)ᵀ and broke non-trivial crystals -- MgO # probe 2026-06-10, 8.25 Ha. See vibeqc.periodic_k_symmetry for # the transport groundwork and pbc_bipole.py for the full note). kmesh_full = _expand_ibz_kmesh_for_ewald_j(system, kmesh, plog) if len(list(kmesh_full.kpoints)) > len(k_points): kmesh = kmesh_full k_points = list(kmesh.kpoints) weights = np.asarray(kmesh.weights, dtype=float) _ir_mapping = np.asarray([], dtype=int) k_points_full = k_points weights_full = weights else: k_points_full = k_points weights_full = weights 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}") if use_ewald_j_split and n_k > 1 and _ir_mapping.size == 0: uniform_w = 1.0 / float(n_k) if not np.allclose(weights, uniform_w, atol=1e-9): raise ValueError( "use_ewald_j_split at multi-k requires uniform full-mesh " "weights or an IBZ-reduced Monkhorst-Pack mesh carrying " "ir_mapping metadata so the driver can expand it. " f"Got non-uniform weights = {weights.tolist()}." ) # ---- Exchange/gauge resolution (option (b) Phase 4b, 2026-06-11) -- # Mirrors run_pbc_bipole_rhf; per-spin exchange split at 3D Γ: # K_s = K_SR(erfc w; D_s) + K_LR(D_s) + (ξ_M - pi/(Vw^2)).S.D_s.S # (PySCF UHF exxdiv convention: vk_s += ξ.S.D_s.S per spin). if exchange_exxdiv not in ("ewald", "none"): raise ValueError( f"run_pbc_bipole_uhf: exchange_exxdiv must be 'ewald' or " f"'none'; got {exchange_exxdiv!r}" ) _x_split_auto = use_exchange_ewald_split is None exchange_split_active = ( bool(use_ewald_j_split) if _x_split_auto else bool(use_exchange_ewald_split) ) if exchange_split_active and not use_ewald_j_split: raise ValueError( "run_pbc_bipole_uhf: use_exchange_ewald_split=True requires " "the Ewald J split (use_ewald_j_split=True)." ) # Multi-k split (option (b) Phase 3): needs the true Monkhorst- # Pack dimensions (q-channel tables, BvK-torus fold, supercell # Madelung); ad-hoc k-lists are rejected. _bvk_mesh: Optional[Tuple[int, int, int]] = None if exchange_split_active and n_k > 1: _mesh_attr = tuple(int(x) for x in getattr(kmesh, "mesh", (1, 1, 1))) if int(np.prod(_mesh_attr)) != n_k: if _x_split_auto: plog.info( " multi-k corrected exchange gauge needs a " "Monkhorst-Pack mesh (BvK-torus fold + supercell ξ_M); " "this ad-hoc k-list has no mesh metadata -> falling back " "to the legacy gauge. Pass a monkhorst_pack(...) mesh " "for the corrected gauge." ) exchange_split_active = False else: raise ValueError( "run_pbc_bipole_uhf: the Ewald exchange split at multi-k " "requires a Monkhorst-Pack BlochKMesh carrying its mesh " f"dimensions (got mesh={_mesh_attr} for {n_k} k-points). " "Build the mesh via monkhorst_pack(...); ad-hoc k-point " "lists are not supported on the corrected gauge." ) else: _bvk_mesh = _mesh_attr warn_bipole_legacy_multik_gauge(system, exchange_split_active, n_k, plog) warn_bipole_charged_cell(system, plog) _xi_madelung = 0.0 if exchange_split_active and exchange_exxdiv == "ewald": if n_k > 1: from .bipole_fock_ewald import probe_charge_madelung_supercell assert _bvk_mesh is not None _xi_madelung = probe_charge_madelung_supercell(system, _bvk_mesh) else: from .bipole_fock_ewald import probe_charge_madelung _xi_madelung = probe_charge_madelung(system) plog.info( f"PBC BIPOLE UHF (CRYSTAL-gauge) / cutoff {lat_opts.cutoff_bohr:.2f} bohr" ) if exchange_split_active: plog.info( f" Gauge: corrected -- per-spin Ewald exchange split " f"(exxdiv={exchange_exxdiv}" + ( f", ξ_M = {_xi_madelung:.6f} Ha" if exchange_exxdiv == "ewald" else "" ) + "); full Bloch density; spheropole omitted" ) plog.info(f" n_alpha = {n_alpha}, n_beta = {n_beta}, multiplicity = {mult}") plog.info( f" F^2e (J + K) : " f"{'EWALD_J_SPLIT' if use_ewald_j_split else lat_opts_2e.coulomb_method.name}" f"{' (auto)' if use_ewald_j_split_auto else ''}" ) plog.info( f"k-mesh: {n_k} k-point{'s' if n_k != 1 else ''}, " f"weights sum = {weights.sum():.4f}" ) ewald_options_1e: Optional[EwaldOptions] = None omega_used: Optional[float] = None ewald_cell_volume: Optional[float] = None ewald_k_max: Optional[float] = None if system.dim == 3: from .bipole_ext_el_pole import ( crystal_default_ewald_alpha, crystal_ewald_reciprocal_cutoff, ) V_cell = float( abs( np.linalg.det(np.asarray(system.lattice, dtype=float)), ) ) ewald_cell_volume = V_cell omega_used = ( float(ewald_omega) if ewald_omega is not None else crystal_default_ewald_alpha(V_cell) ) ewald_k_max = crystal_ewald_reciprocal_cutoff(V_cell) ewald_options_1e = _crystal_ewald_options( lat_opts_1e, alpha_bohr_inv=omega_used, tolerance=float(ewald_precision), recip_cutoff_bohr_inv=ewald_k_max, ) plog.info( f" Ewald state: alpha = {omega_used:.6f} bohr^-1, " f"real_cutoff = {lat_opts_1e.nuclear_cutoff_bohr:.2f} bohr, " f"K_max = {ewald_k_max:.2f} bohr^-1, " f"tol = {float(ewald_precision):.0e}" ) with plog.stage( "integrals_lattice", detail=f"S/T/V at cutoff {lat_opts.cutoff_bohr:.2f} bohr", ): _use_sym = bool(getattr(getattr(system, "symmetry", None), "operations", None)) if _use_sym: ops = system.symmetry.operations cells = direct_lattice_cells(system, lat_opts_2e.cutoff_bohr) plog.info( f"S/T integrals: symmetry-reduced path " f"(SG {system.symmetry.international_symbol}, " f"{system.symmetry.order} ops, " f"{len(cells)} lattice cells)" ) _, S_blocks = compute_overlap_lattice_reduced( basis, system, lat_opts_2e, ops, ) S_lat = make_lattice_matrix_set( basis.nbasis, cells, [np.asarray(b, dtype=float) for b in S_blocks] ) _, T_blocks = compute_kinetic_lattice_reduced( basis, system, lat_opts_2e, ops, ) T_lat = make_lattice_matrix_set( basis.nbasis, cells, [np.asarray(b, dtype=float) for b in T_blocks] ) else: S_lat = compute_overlap_lattice(basis, system, lat_opts_2e) T_lat = compute_kinetic_lattice(basis, system, lat_opts_2e) v_ne_lr_cache = None if ( system.dim == 3 and ewald_options_1e is not None and v_ne_grid_options is None ): V_lat, v_ne_lr_cache = _compute_nuclear_lattice_ewald_reciprocal_ft( basis, system, lat_opts_1e, ewald_options_1e, S_lat, precision=ewald_precision, K_max=ewald_k_max, ) else: v_ne_grid = ( v_ne_grid_options if v_ne_grid_options is not None else (_default_bipole_v_ne_grid_options() if system.dim == 3 else None) ) V_lat = compute_nuclear_lattice_dispatch( basis, system, lat_opts_1e, grid_options=v_ne_grid, ewald_options=ewald_options_1e, ) cells = list(S_lat.cells) plog.info(f"n_cells in lattice sum = {len(cells)}") # Lattice-fold guard + wide density list under the corrected gauge # (rationale: run_pbc_bipole_rhf). if exchange_split_active: from .pbc_bipole_common import s_fold_truncation_drift _s_drift = s_fold_truncation_drift( basis, system, lat_opts_2e, k_points=(k_points if n_k > 1 else None), ) _s_label = "S(k) fold truncation (max over mesh)" if n_k > 1 else "S(Γ) fold truncation" if _s_drift > 1e-2: plog.info( f" WARNING: {_s_label} {_s_drift:.1e} -- lattice " f"sums badly under-converged for this basis's AO tails; " f"absolute energies UNRELIABLE. Increase cutoff_bohr." ) elif _s_drift > 1e-4: plog.info( f" note: {_s_label} {_s_drift:.1e} -- expect " f"~{_s_drift:.0e}-scale absolute-energy truncation" ) cells_density = list( direct_lattice_cells(system, 2.0 * float(lat_opts_2e.cutoff_bohr)) ) plog.info( f" density cell list: {len(cells_density)} cells (2x cutoff)" ) else: cells_density = cells from .linear_dependence import scf_preflight_overlap_check S_k_list: List[np.ndarray] = [] Hcore_k_list: List[np.ndarray] = [] X_k_list: List[np.ndarray] = [] 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_pbc_bipole_uhf: canonical orth at k={k_idx} " f"dropped too many directions (n_alpha={n_alpha}, " f"n_beta={n_beta}, n_kept={n_kept})" ) S_k_list.append(S_k) Hcore_k_list.append(H_k) X_k_list.append(X_k) if ewald_options_1e is not None: e_nuc = float(ewald_nuclear_repulsion(system, ewald_options_1e)) else: e_nuc = float(nuclear_repulsion_per_cell(system, lat_opts_1e)) plog.info(f"E_nuc per cell ({lat_opts_1e.coulomb_method.name}) = {e_nuc:+.10f} Ha") 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) def _spin_density( C_per_k_local: Sequence[np.ndarray], n_occ_each: int, ) -> LatticeMatrixSet: 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) result = real_space_density_from_kpoints_fractional( C_per_k_local, occ_per_k, kmesh, cells_density, ) if not exchange_split_active: _zero_cross_cell_density(result, nbf, n_k) return result D_alpha_real = _spin_density(C_alpha_per_k, n_alpha) D_beta_real = _spin_density(C_beta_per_k, n_beta) # --- Smearing occupation helpers (open-shell: per-spin mu) --- from .smearing.fermi_dirac import fermi_dirac_occupations_per_k as _fd_per_k def _occupations_per_spin( eps_spin_per_k: Sequence[np.ndarray], n_spin: int, ): """Compute per-spin fractional occupations via Fermi-Dirac.""" if smearing_T <= 0.0 or n_spin == 0: occ = [] for eps in eps_spin_per_k: o = np.zeros(eps.shape[0], dtype=float) o[:n_spin] = 1.0 occ.append(o) return occ, 0.0, 0.0 # The shared closed-shell helper returns occupations in [0, 2]; # divide by 2 for the single-spin UHF convention. occ_double, mu, entropy_double = _fd_per_k( eps_spin_per_k, weights, float(2 * n_spin), smearing_T, ) occ = [np.asarray(o, dtype=float) * 0.5 for o in occ_double] return occ, mu, entropy_double * 0.5 occ_alpha_per_k, mu_alpha, entropy_alpha = _occupations_per_spin( eps_alpha_per_k, n_alpha ) occ_beta_per_k, mu_beta, entropy_beta = _occupations_per_spin( eps_beta_per_k, n_beta ) entropy = entropy_alpha + entropy_beta if smearing_T > 0.0: D_alpha_real = real_space_density_from_kpoints_fractional( C_alpha_per_k, occ_alpha_per_k, kmesh, cells_density ) D_beta_real = real_space_density_from_kpoints_fractional( C_beta_per_k, occ_beta_per_k, kmesh, cells_density ) if not exchange_split_active: _zero_cross_cell_density(D_alpha_real, D_alpha_real.blocks[0].shape[0], n_k) _zero_cross_cell_density(D_beta_real, D_beta_real.blocks[0].shape[0], n_k) # Caller-supplied warm-start spin densities take precedence over # the SAD/Hcore guess engine. Both init_alpha and init_beta must # be provided together (or both None). Block ordering matches the # canonical ``direct_lattice_cells(kmesh)`` ordering -- same # contract as the RHF driver. Used by the NEB driver for # within-image density warm-start for periodic NEB. if (init_alpha is not None) != (init_beta is not None): raise ValueError( "run_pbc_bipole_uhf: init_alpha and init_beta must be " "provided together (both None or both populated)" ) if init_alpha is not None and init_beta is not None: blocks_a = list(init_alpha) blocks_b = list(init_beta) if len(blocks_a) != len(D_alpha_real.cells): raise ValueError( f"run_pbc_bipole_uhf: init_alpha has {len(blocks_a)} " f"blocks; expected {len(D_alpha_real.cells)}" ) if len(blocks_b) != len(D_beta_real.cells): raise ValueError( f"run_pbc_bipole_uhf: init_beta has {len(blocks_b)} " f"blocks; expected {len(D_beta_real.cells)}" ) for g_idx, (ba, bb) in enumerate(zip(blocks_a, blocks_b)): D_alpha_real.set_block(g_idx, np.asarray(ba, dtype=float)) D_beta_real.set_block(g_idx, np.asarray(bb, dtype=float)) plog.info("initial guess: caller-supplied spin densities (warm-start)") initial_density_is_local = True density_from_c_per_k = False else: guess = getattr(opts, "initial_guess", InitialGuess.HCORE) # ATOMSPIN: per-atom +1/-1/0 broken-symmetry seed. When set it must # reach the open-shell engine (which assembles the block-diagonal # broken-symmetry density); the even-electron closed-shell shortcut # below would wash it out to a spin-symmetric 50/50 split, so skip # that shortcut whenever a spin pattern is requested. _atomic_spins = getattr(opts, "atomic_spins", None) or None # READ likewise carries the prior's *per-spin* g=0 densities, which the # even-electron closed-shell shortcut would collapse to a 50/50 split -- # skip the shortcut for READ too so the prior magnetisation survives. _is_read = guess == InitialGuess.READ _needs_open_context = guess in { InitialGuess.SAP, InitialGuess.PATOM, InitialGuess.HUECKEL, InitialGuess.MINAO, } _patom_seed_pending = guess == InitialGuess.PATOM D_guess = None if ( n_elec % 2 == 0 and _atomic_spins is None and not _is_read and not _needs_open_context ): # CRYSTAL's UHF PATIRR/SAD starts from the total atomic SAD with # zero summed spin density, then the requested spin state is # enforced by the alpha/beta occupations after the first Fock # diagonalisation. Mirror that convention for CYC0 parity. D_total_guess = initial_density_closed_shell( system.unit_cell_molecule(), basis, n_elec // 2, guess, is_periodic=True, ) if D_total_guess is not None: D_guess = ( 0.5 * np.asarray(D_total_guess, dtype=float), 0.5 * np.asarray(D_total_guess, dtype=float), ) if D_guess is None: _seed_guess = InitialGuess.SAD if _patom_seed_pending else guess D_guess = initial_densities_open_shell( system.unit_cell_molecule(), basis, n_alpha, n_beta, _seed_guess, is_periodic=True, periodic_system=system, lattice_opts=lat_opts, atomic_spins=_atomic_spins, read_density_alpha=getattr(opts, "read_density_alpha", None), read_density_beta=getattr(opts, "read_density_beta", None), read_path=getattr(opts, "read_path", ""), ) initial_density_is_local = D_guess is not None if D_guess is not None: plog.info(f"initial guess: {guess.name} (g=0 spin densities)") D_a0, D_b0 = D_guess zero_a = np.zeros_like(D_a0, dtype=float) zero_b = np.zeros_like(D_b0, dtype=float) for g_idx in range(len(D_alpha_real.cells)): is_g0 = ( np.asarray(D_alpha_real.cells[g_idx].index, dtype=int) == np.array([0, 0, 0]) ).all() D_alpha_real.set_block(g_idx, D_a0 if is_g0 else zero_a) D_beta_real.set_block(g_idx, D_b0 if is_g0 else zero_b) else: plog.info(f"initial guess: {guess.name} (Hcore-diag per k)") density_from_c_per_k = not initial_density_is_local if init_alpha is not None and init_beta is not None: _patom_seed_pending = False 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_pbc_bipole_uhf: damping must be in [0,1); got {damping}") 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)), ) use_diis = bool(opts.use_diis) diis_start_iter = int(opts.diis_start_iter) accel: Optional[MultiKPeriodicUHFAccelerator] = ( MultiKPeriodicUHFAccelerator(opts) if use_diis else None ) level_shift_static = float(getattr(opts, "level_shift", 0.0)) if level_shift_schedule is not None and not isinstance( level_shift_schedule, LevelShiftSchedule, ): raise TypeError( f"level_shift_schedule must be a LevelShiftSchedule or None; " f"got {type(level_shift_schedule).__name__}" ) if level_shift_schedule is not None: plog.info(f"level_shift_schedule: {level_shift_schedule.as_list()}") # CRYSTAL-style FMIXING (per-spin, per-k). fock_mixing_value = float(getattr(opts, "fock_mixing", 0.0)) if not (0.0 <= fock_mixing_value < 1.0): raise ValueError( f"run_pbc_bipole_uhf: fock_mixing must be in [0, 1); " f"got {fock_mixing_value}" ) if fock_mixing_value != 0.0: plog.info( f"fock mixing: CRYSTAL FMIXING " f"{100.0 * fock_mixing_value:.1f}% " "(previous Fock matrix weight)" ) F_alpha_prev_mixed: Optional[List[np.ndarray]] = None F_beta_prev_mixed: Optional[List[np.ndarray]] = None # SPINLOCK PATTERN_HOLD reuses the per-k MOM machinery (same kernel as # use_mom), gated to cycles 2..spinlock_iterations, to hold the seeded # broken-symmetry occupied set then release -- protecting an ATOMSPIN seed. _spinlock_pattern_hold = ( getattr(opts, "spinlock_mode", SpinlockMode.OFF) == SpinlockMode.PATTERN_HOLD and int(getattr(opts, "spinlock_iterations", 0)) > 0 ) _spinlock_iters = int(getattr(opts, "spinlock_iterations", 0)) if use_mom: plog.info("MOM (Maximum Overlap Method): ON") elif _spinlock_pattern_hold: plog.info(f"SPINLOCK PATTERN_HOLD: MOM-hold for {_spinlock_iters} cycles") C_prev_occ_alpha_per_k = None C_prev_occ_beta_per_k = None if use_oda and use_diis: raise ValueError( "run_pbc_bipole_uhf: use_oda and use_diis are mutually exclusive" ) if use_oda: if not (0.0 < oda_trust_lambda_max <= 1.0): raise ValueError( f"oda_trust_lambda_max must be in (0, 1]; got {oda_trust_lambda_max}" ) plog.info( f"ODA (Optimal Damping): ON (+1 Fock build/iter, " f"trust lambda_max = {oda_trust_lambda_max})" ) j_lr_cache = v_ne_lr_cache if use_ewald_j_split: if system.dim != 3: raise ValueError( f"use_ewald_j_split requires dim=3 (3D periodic). Got dim={system.dim}." ) from .bipole_fock_ewald import _build_j_long_range_cache assert omega_used is not None cells_r_cart_arr = np.array( [np.asarray(c.r_cart, dtype=float) for c in cells], dtype=float, ) if j_lr_cache is None: j_lr_cache = _build_j_long_range_cache( basis, system, cells_r_cart_arr, omega_used, ewald_precision, K_max=ewald_k_max, ) elif j_lr_cache.ft_per_cell.shape[0] != len(cells): raise RuntimeError( "prebuilt V_ne/J^LR cache has a different cell count " f"({j_lr_cache.ft_per_cell.shape[0]}) from S_lat " f"({len(cells)})" ) plog.info( f" J^LR cache: {j_lr_cache.K_vectors.shape[0]} K-vectors, " f"{j_lr_cache.ft_per_cell.shape[0]} lattice cells" ) # Multi-k split: per-(k,k′) q-channel tables for the per-spin LR # exchange (option (b) Phase 3). Shares the J^LR w/K_max envelope; # both spins consume the same density-independent tables. x_lr_cache = None if exchange_split_active and n_k > 1: from .bipole_fock_ewald import build_k_exchange_long_range_cache assert j_lr_cache is not None and ewald_k_max is not None x_lr_cache = build_k_exchange_long_range_cache( basis, system, j_lr_cache, K_max=ewald_k_max, ) plog.info( f" K^LR q-channels: {n_k} distinct q = k-k′ shifts on the " f"shared K_max = {ewald_k_max:.2f} bohr⁻¹ envelope (per spin)" ) def _split_k_density_list(density: LatticeMatrixSet) -> List[np.ndarray]: """Per-k (single-spin) density matrices for the split paths. Home block at Γ; exact BvK-torus fold at multi-k (see ``bvk_torus_density_matrices``) -- exact for orbital, SAD-local, damped, ODA-mixed, and warm-start spin densities alike. """ if n_k == 1: return [home_cell_block(density).astype(complex)] assert _bvk_mesh is not None return bvk_torus_density_matrices(density, k_points, _bvk_mesh) # Per-spin incremental/differential J_SR+K_SR accumulators (opt-in; # see run_pbc_bipole_rhf). The corrected gauge builds jk_a + jk_b # separately, so each spin gets its own ΔD chain. Corrected gauge + # DIIS only. incremental_jk_alpha = None incremental_jk_beta = None if use_incremental_fock: if exchange_split_active and not use_oda: from .bipole_fock_ewald import IncrementalJK incremental_jk_alpha = IncrementalJK() incremental_jk_beta = IncrementalJK() plog.info( " incremental Fock (per-spin differential J_SR/K_SR via " "ΔD density-envelope screening): ON" ) else: plog.info( " incremental Fock requested but inactive " "(needs the corrected gauge + DIIS, not ODA)" ) # The UHF two-electron Fock assembly is routed through # pbc_bipole_fock.build_bipole_unrestricted_fock below. # ---- Multipole far-field config (resolve once before SCF loop) ----- from .bipole_fock_multipole import ( # noqa: E402 BipoleMultipoleConfig, resolve_multipole_config, ) if exchange_split_active and use_multipole_far_field: raise NotImplementedError( "run_pbc_bipole_uhf: the multipole far-field J replacement has " "not been re-validated under the corrected gauge. Pass " "use_exchange_ewald_split=False to combine it with the legacy " "gauge, or omit use_multipole_far_field." ) _mp_config = resolve_multipole_config( system, basis, lat_opts_2e, user_enable=(False if exchange_split_active else use_multipole_far_field), multipole_l_max=multipole_l_max, ) if _mp_config.enabled: plog.info( f" BIPOLE multipole far-field: ENABLED " f"(L_max={_mp_config.L_max}, R_bipole={_mp_config.R_bipole:.1f} bohr, " f"n_cells={len(_mp_config.cache.cells) if _mp_config.cache else 0})" ) else: plog.info( f" BIPOLE multipole far-field: off " f"(R_bipole={_mp_config.R_bipole:.1f} bohr, " f"cutoff={lat_opts_2e.cutoff_bohr:.1f} bohr)" ) # SYM3b Fock symmetry enforcement is OPT-IN ONLY -- rationale # (boundary truncation asymmetry) lives on the shared resolver. _fock_sym_map, _rep_cell_indices = resolve_bipole_fock_symmetry( system, basis, lat_opts_2e, use_fock_symmetry, use_fock_symmetry_reduce, plog, per_spin=True, ) # ---- Shared unrestricted Fock-build context (M2c unification) ------- # Bundle the per-run invariants the inline UHF Fock build captured. # The wrapper below is intentionally placed after multipole and symmetry # resolution, before the PATOM in-field step and SCF loop first call it. _fock_ctx = BipoleFockContext( basis=basis, system=system, lat_opts_2e=lat_opts_2e, use_ewald_j_split=use_ewald_j_split, exchange_split_active=exchange_split_active, n_k=n_k, omega_used=omega_used, ewald_precision=ewald_precision, ewald_cell_volume=ewald_cell_volume, n_elec=n_elec, xi_madelung=_xi_madelung, j_lr_cache=j_lr_cache, x_lr_cache=x_lr_cache, incremental_jk=None, rep_cell_indices=_rep_cell_indices, fock_sym_map=_fock_sym_map, mp_config=_mp_config, s_lat=S_lat, s_k_list=S_k_list, k_points=k_points, weights=weights, k_points_full=k_points_full, weights_full=weights_full, ir_mapping=_ir_mapping, bvk_mesh=_bvk_mesh, n_occ=n_alpha, plog=plog, sr_image_extent=sr_image_extent_bohr, ) def _build_fock_for_density( D_alpha: LatticeMatrixSet, D_beta: LatticeMatrixSet, *, coeffs_alpha_for_rho: Optional[Sequence[np.ndarray]], coeffs_beta_for_rho: Optional[Sequence[np.ndarray]], use_incremental: bool = True, ) -> BipoleUnrestrictedFockBuild: return build_bipole_unrestricted_fock( _fock_ctx, D_alpha, D_beta, hcore_k_list=Hcore_k_list, n_alpha=n_alpha, n_beta=n_beta, coeffs_alpha_for_rho=coeffs_alpha_for_rho, coeffs_beta_for_rho=coeffs_beta_for_rho, occupations_alpha_per_k=occ_alpha_per_k, occupations_beta_per_k=occ_beta_per_k, smearing_temperature=smearing_T, incremental_jk_alpha=incremental_jk_alpha, incremental_jk_beta=incremental_jk_beta, use_incremental=use_incremental, ) if _patom_seed_pending: plog.info("initial guess: PATOM (SAD + one BIPOLE in-field step)") patom_fock = _build_fock_for_density( D_alpha_real, D_beta_real, coeffs_alpha_for_rho=None, coeffs_beta_for_rho=None, use_incremental=False, ) C_alpha_per_k = [] eps_alpha_per_k = [] C_beta_per_k = [] eps_beta_per_k = [] for idx in range(n_k): C_a, eps_a = _diag_in_orth_basis( patom_fock.f_alpha_k_list[idx], X_k_list[idx], ) C_b, eps_b = _diag_in_orth_basis( patom_fock.f_beta_k_list[idx], X_k_list[idx], ) C_alpha_per_k.append(C_a) eps_alpha_per_k.append(eps_a) C_beta_per_k.append(C_b) eps_beta_per_k.append(eps_b) occ_alpha_per_k, mu_alpha, entropy_alpha = _occupations_per_spin( eps_alpha_per_k, n_alpha ) occ_beta_per_k, mu_beta, entropy_beta = _occupations_per_spin( eps_beta_per_k, n_beta ) entropy = entropy_alpha + entropy_beta if smearing_T > 0.0: D_alpha_real = real_space_density_from_kpoints_fractional( C_alpha_per_k, occ_alpha_per_k, kmesh, cells_density ) D_beta_real = real_space_density_from_kpoints_fractional( C_beta_per_k, occ_beta_per_k, kmesh, cells_density ) if not exchange_split_active: _zero_cross_cell_density( D_alpha_real, D_alpha_real.blocks[0].shape[0], n_k ) _zero_cross_cell_density( D_beta_real, D_beta_real.blocks[0].shape[0], n_k ) else: 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 = None D_beta_prev = None initial_density_is_local = False density_from_c_per_k = True plog.banner("SCF (PBC BIPOLE UHF, direct-space)") plog.info(" iter energy (Ha) dE ||[F,DS]|| DIIS") # ---- DFT+U setup (Increment 4d-bipole) ------------------------------ # Translate user-facing HubbardSite objects to the C++ types + AO # index lists once per SCF call. ao_group_indices is geometry- # invariant (depends only on shell layout per atom Z + basis name), # so it's safe to pre-compute here. dft_plus_u_sites_cxx: List = [] dft_plus_u_ao_groups: List[List[int]] = [] if dft_plus_u: from ._vibeqc_core import _HubbardSiteCxx from .dft_plus_u import ao_group_indices ao_groups_map = ao_group_indices(basis) for site in dft_plus_u: key = (site.atom_index, site.l) if key not in ao_groups_map: raise ValueError( f"run_pbc_bipole_uhf: HubbardSite{key} has no AOs " f"in the basis. Available channels: " f"{sorted(ao_groups_map.keys())}" ) dft_plus_u_sites_cxx.append( _HubbardSiteCxx(site.atom_index, site.l, site.U_eff_hartree) ) dft_plus_u_ao_groups.append(ao_groups_map[key]) scf_trace: List[SCFIteration] = [] energy_components: List[PBCBipoleEnergyComponents] = [] E_prev = 0.0 E_elec = 0.0 e_dft_plus_u = 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 # SPINLOCK PATTERN_HOLD: the accelerator (DIIS / EDIIS / ADIIS / # KDIIS -- whatever MultiKPeriodicUHFAccelerator resolved) is # suspended (no history recorded, no extrapolation, damping stays # live) while the hold is active. Fock extrapolation across # held-window iterates steers the SCF toward the symmetric attractor # by continuous orbital rotation -- a collapse the # occupation-selecting MOM hold cannot see -- and poisons the # post-release history with out-of-basin iterates. The history # starts fresh at release. hold_active = _spinlock_pattern_hold and iter_idx <= _spinlock_iters diis_active = ( use_diis and iter_idx >= diis_start_iter and not hold_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 d_used_is_damped = iter_idx > 1 and damping > 0.0 and not diis_active d_used_from_coeffs = ( density_from_c_per_k and not (initial_density_is_local and iter_idx == 1) and not d_used_is_damped ) fock_build = _build_fock_for_density( D_alpha_used, D_beta_used, coeffs_alpha_for_rho=(C_alpha_per_k if d_used_from_coeffs else None), coeffs_beta_for_rho=(C_beta_per_k if d_used_from_coeffs else None), ) F_alpha_k_list = fock_build.f_alpha_k_list F_beta_k_list = fock_build.f_beta_k_list # ---- DFT+U: per-spin per-k Fock contribution ----------------- # n_s = S_k w_k Re[(S(k) P_s(k) S(k))_(A,l)]; V_AO_s = U_eff # (1/2 - n_s); per-k Fock += S(k) V_AO_s S(k). The per-spin # densities P_s(k) come from Bloch-summing the same lattice # density that fock_build saw. e_dft_plus_u = 0.0 if dft_plus_u_sites_cxx: from ._vibeqc_core import ( _compute_dft_plus_u_multi_k_per_spin_cxx, ) P_split_a_for_u: Optional[List[np.ndarray]] = None P_split_b_for_u: Optional[List[np.ndarray]] = None if exchange_split_active: # Unprojected Bloch fold: S_g over the full cell list # overcounts -- BvK representatives instead (home block # at Γ; exact torus fold at multi-k). P_split_a_for_u = _split_k_density_list(D_alpha_used) P_split_b_for_u = _split_k_density_list(D_beta_used) P_alpha_k_for_U: List[np.ndarray] = [] P_beta_k_for_U: List[np.ndarray] = [] for k_idx in range(n_k): if P_split_a_for_u is not None: Pa_k = P_split_a_for_u[k_idx] Pb_k = P_split_b_for_u[k_idx] else: k_arr = np.asarray(k_points[k_idx], dtype=float) Pa_k = _bloch_sum_blocks( D_alpha_used.blocks, D_alpha_used.cells, k_arr, ) Pb_k = _bloch_sum_blocks( D_beta_used.blocks, D_beta_used.cells, k_arr, ) Pa_k = 0.5 * (Pa_k + Pa_k.conj().T) Pb_k = 0.5 * (Pb_k + Pb_k.conj().T) P_alpha_k_for_U.append(Pa_k) P_beta_k_for_U.append(Pb_k) E_a, V_AO_a = _compute_dft_plus_u_multi_k_per_spin_cxx( dft_plus_u_sites_cxx, dft_plus_u_ao_groups, S_k_list, P_alpha_k_for_U, list(weights), ) E_b, V_AO_b = _compute_dft_plus_u_multi_k_per_spin_cxx( dft_plus_u_sites_cxx, dft_plus_u_ao_groups, S_k_list, P_beta_k_for_U, list(weights), ) e_dft_plus_u = float(E_a) + float(E_b) V_AO_a_cmplx = np.asarray(V_AO_a, dtype=complex) V_AO_b_cmplx = np.asarray(V_AO_b, dtype=complex) for k_idx in range(n_k): S_k = S_k_list[k_idx] F_alpha_k_list[k_idx] = F_alpha_k_list[k_idx] + ( S_k @ V_AO_a_cmplx @ S_k ) F_beta_k_list[k_idx] = F_beta_k_list[k_idx] + (S_k @ V_AO_b_cmplx @ S_k) F_alpha_k_list[k_idx] = 0.5 * ( F_alpha_k_list[k_idx] + F_alpha_k_list[k_idx].conj().T ) F_beta_k_list[k_idx] = 0.5 * ( F_beta_k_list[k_idx] + F_beta_k_list[k_idx].conj().T ) D_total_used = _combine_density_sets( basis, system, lat_opts_2e, D_alpha_used, D_beta_used, ) E_kin = _lattice_contract(D_total_used, T_lat, operator_name="T") E_ne = _lattice_contract(D_total_used, V_lat, operator_name="V_ne") E_2e = fock_build.e_2e_k_correction + 0.5 * ( _lattice_contract( D_alpha_used, fock_build.f2e_alpha_real, operator_name="F2e_alpha", ) + _lattice_contract( D_beta_used, fock_build.f2e_beta_real, operator_name="F2e_beta", ) ) E_elec = E_kin + E_ne + E_2e grad_norm_sum = 0.0 error_alpha_k_list: List[np.ndarray] = [] error_beta_k_list: List[np.ndarray] = [] D_alpha_k_list: List[np.ndarray] = [] D_beta_k_list: List[np.ndarray] = [] D_k_split_guess_a: Optional[List[np.ndarray]] = None D_k_split_guess_b: Optional[List[np.ndarray]] = None if exchange_split_active and initial_density_is_local and iter_idx == 1: # BvK representatives for local AND wide warm-start storage # (home block at Γ, exact torus fold at multi-k) -- a S_g # fold over the full cell list would overcount wide # warm-start blocks. SAD-local guesses give identical # values either way (only g = 0 contributes). D_k_split_guess_a = _split_k_density_list(D_alpha_used) D_k_split_guess_b = _split_k_density_list(D_beta_used) for idx in range(n_k): if initial_density_is_local and iter_idx == 1: if D_k_split_guess_a is not None and D_k_split_guess_b is not None: D_a_k = D_k_split_guess_a[idx] D_b_k = D_k_split_guess_b[idx] else: k_arr = np.asarray(k_points[idx], dtype=float) D_a_k = _bloch_sum_blocks( D_alpha_used.blocks, D_alpha_used.cells, k_arr, ) D_b_k = _bloch_sum_blocks( D_beta_used.blocks, D_beta_used.cells, k_arr, ) D_a_k = 0.5 * (D_a_k + D_a_k.conj().T) D_b_k = 0.5 * (D_b_k + D_b_k.conj().T) else: C_a = C_alpha_per_k[idx] C_b = C_beta_per_k[idx] if smearing_T <= 0.0: 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 else: occ_a = np.asarray(occ_alpha_per_k[idx], dtype=float) occ_b = np.asarray(occ_beta_per_k[idx], dtype=float) C_a_full = np.asarray(C_a, dtype=np.complex128) C_b_full = np.asarray(C_b, dtype=np.complex128) D_a_k = (C_a_full * occ_a[None, :]) @ C_a_full.conj().T D_b_k = (C_b_full * occ_b[None, :]) @ C_b_full.conj().T D_alpha_k_list.append(D_a_k) D_beta_k_list.append(D_b_k) S_k = S_k_list[idx] F_a_k = F_alpha_k_list[idx] F_b_k = F_beta_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 += float(weights[idx]) * float( np.sqrt(np.linalg.norm(err_a) ** 2 + np.linalg.norm(err_b) ** 2) ) E_total = float(E_elec) + e_nuc # EXT EL-SPHEROPOLE -- uses total (alpha+beta) density. D_total_used = _combine_density_sets( basis, system, lat_opts_2e, D_alpha_used, D_beta_used ) # EXT EL-SPHEROPOLE -- a 3D-Ewald-gauge correction, identically # zero in the direct (non-Ewald) gauge used for dim<3, and # OMITTED under the corrected gauge (double-count). if system.dim == 3 and not exchange_split_active: E_sphero = compute_ext_el_spheropole(D_total_used, basis, system, lat_opts) E_total += E_sphero else: E_sphero = None free_energy = E_total - smearing_T * entropy dE = free_energy - E_prev if iter_idx > 1 else 0.0 check_scf_divergence( "run_pbc_bipole_uhf", iter_idx, free_energy, 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(free_energy), delta_e=float(dE), grad_norm=float(grad_norm_sum), diis_subspace=diis_sub, ) ) plog.iteration( iter_idx, energy=float(free_energy), dE=float(dE), grad=float(grad_norm_sum), diis=diis_sub, ) energy_components.append( PBCBipoleEnergyComponents( iter=int(iter_idx), e_total=float(E_total), e_electronic=float(E_elec), e_kinetic=float(E_kin), e_nuclear_attraction=float(E_ne), e_two_electron=float(E_2e), e_nuclear_repulsion=float(e_nuc), e_bielet_zone_ee=(None if use_ewald_j_split else float(E_2e)), e_j_short_range=fock_build.e_j_short_range, e_j_long_range=fock_build.e_j_long_range, e_exchange=fock_build.e_exchange, e_ext_el_spheropole=E_sphero, ) ) plog.energy_decomposition( iter_idx, E_kin=float(E_kin), E_ne=float(E_ne), E_2e=float(E_2e), E_elec=float(E_elec), E_nuc=float(e_nuc), ) converged = ( iter_idx > 1 and abs(dE) < float(opts.conv_tol_energy) and grad_norm_sum < float(opts.conv_tol_grad) ) # Skipped entirely (not even recorded) while the PATTERN_HOLD window # is active; see the hold_active note at the loop head. if accel is not None and not hold_active: if exchange_split_active: # Unprojected Bloch fold: S_g over the full cell list # overcounts -- BvK representatives per k instead (home # block at Γ; exact torus fold at multi-k). Mirrors # the RHF accelerator fold; only the bridged # EDIIS/ADIIS modes consume these densities. density_alpha_k_list = _split_k_density_list(D_alpha_used) density_beta_k_list = _split_k_density_list(D_beta_used) else: 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=free_energy, 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), ) # On the converged iteration, diagonalise the *physical* Fock # F(D) -- not the extrapolated one -- so the final orbitals/ # density stay on the converged fixed point. A near-machine- # zero DIIS error history (SCF nailing the solution in one # step) makes the Pulay B-matrix singular; the degenerate # solve then returns a garbage extrapolated Fock whose Aufbau # diagonalisation can occupy the wrong orbital. See the RHF # twin in pbc_bipole.py and # tests/test_pbc_bipole_diis_converged_basin.py. if diis_active and not converged: F_alpha_k_list = F_a_ex F_beta_k_list = F_b_ex # --- FMIXING (per-spin, per-k, after DIIS, before level-shift) # Skipped on the converged iteration (see DIIS note above). if fock_mixing_value != 0.0 and not converged: if F_alpha_prev_mixed is not None: for spin_list, prev_list in [ (F_alpha_k_list, F_alpha_prev_mixed), (F_beta_k_list, F_beta_prev_mixed), ]: for idx in range(n_k): F_mixed = (1.0 - fock_mixing_value) * spin_list[ idx ] + fock_mixing_value * prev_list[idx] spin_list[idx] = 0.5 * (F_mixed + F_mixed.conj().T) F_alpha_prev_mixed = [ np.asarray(F, dtype=complex).copy() for F in F_alpha_k_list ] F_beta_prev_mixed = [ np.asarray(F, dtype=complex).copy() for F in F_beta_k_list ] if level_shift_schedule is not None: level_shift_b = level_shift_schedule.at(iter_idx) else: level_shift_b = level_shift_static if level_shift_b != 0.0 and not converged: F_alpha_for_diag: List[np.ndarray] = [] F_beta_for_diag: List[np.ndarray] = [] for idx in range(n_k): S_k = S_k_list[idx] D_a_k = D_alpha_k_list[idx] D_b_k = D_beta_k_list[idx] F_a_shift = ( F_alpha_k_list[idx] + level_shift_b * S_k - (level_shift_b / 2.0) * (S_k @ D_a_k @ S_k) ) F_b_shift = ( F_beta_k_list[idx] + level_shift_b * S_k - (level_shift_b / 2.0) * (S_k @ D_b_k @ S_k) ) F_alpha_for_diag.append(0.5 * (F_a_shift + F_a_shift.conj().T)) F_beta_for_diag.append(0.5 * (F_b_shift + F_b_shift.conj().T)) else: F_alpha_for_diag = F_alpha_k_list F_beta_for_diag = F_beta_k_list new_C_alpha: List[np.ndarray] = [] new_eps_alpha: List[np.ndarray] = [] new_C_beta: List[np.ndarray] = [] new_eps_beta: List[np.ndarray] = [] for idx in range(n_k): C_a, eps_a = _diag_in_orth_basis( F_alpha_for_diag[idx], X_k_list[idx], ) C_b, eps_b = _diag_in_orth_basis( F_beta_for_diag[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) # --- MOM reorder (iter >= 2 only) --- # use_mom holds every cycle; SPINLOCK PATTERN_HOLD holds only cycles # 2..spinlock_iterations, then releases. _mom_this_iter = use_mom or ( _spinlock_pattern_hold and 1 < iter_idx <= _spinlock_iters ) if _mom_this_iter and C_prev_occ_alpha_per_k is not None: for idx in range(n_k): for spin, (C_k, eps_k, n_occ_spin, C_prev_occ_k) in enumerate( [ ( new_C_alpha[idx], new_eps_alpha[idx], n_alpha, C_prev_occ_alpha_per_k[idx], ), ( new_C_beta[idx], new_eps_beta[idx], n_beta, C_prev_occ_beta_per_k[idx], ), ] ): if n_occ_spin == 0: continue S_k = S_k_list[idx] sel = _mom_select( C_k, S_k, C_prev_occ_k, n_occ_spin, eps_new=eps_k, ) n_kept_idx = C_k.shape[1] virt_mask = np.ones(n_kept_idx, dtype=bool) virt_mask[sel] = False virt_sel = np.where(virt_mask)[0] virt_sel = virt_sel[np.argsort(np.real(eps_k[virt_sel]))] order = np.concatenate([sel, virt_sel]) if spin == 0: new_C_alpha[idx] = C_k[:, order] new_eps_alpha[idx] = eps_k[order] else: new_C_beta[idx] = C_k[:, order] new_eps_beta[idx] = eps_k[order] 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 occ_alpha_per_k, mu_alpha, entropy_alpha = _occupations_per_spin( eps_alpha_per_k, n_alpha ) occ_beta_per_k, mu_beta, entropy_beta = _occupations_per_spin( eps_beta_per_k, n_beta ) entropy = entropy_alpha + entropy_beta if smearing_T > 0.0: D_alpha_new = real_space_density_from_kpoints_fractional( C_alpha_per_k, occ_alpha_per_k, kmesh, cells_density ) D_beta_new = real_space_density_from_kpoints_fractional( C_beta_per_k, occ_beta_per_k, kmesh, cells_density ) if not exchange_split_active: _zero_cross_cell_density( D_alpha_new, D_alpha_new.blocks[0].shape[0], n_k ) _zero_cross_cell_density(D_beta_new, D_beta_new.blocks[0].shape[0], n_k) else: D_alpha_new = _spin_density(C_alpha_per_k, n_alpha) D_beta_new = _spin_density(C_beta_per_k, n_beta) # --- ODA mixing (extra Fock build) --- if use_oda: fock_naive = _build_fock_for_density( D_alpha_new, D_beta_new, coeffs_alpha_for_rho=C_alpha_per_k, coeffs_beta_for_rho=C_beta_per_k, use_incremental=False, # off the per-iter ΔD chain ) oda_step = _compute_oda_lambda( D_alpha_used, D_alpha_new, F_alpha_k_list, fock_naive.f_alpha_k_list, [np.asarray(k) for k in k_points], weights, trust_lambda_max=oda_trust_lambda_max, ) _oda_mix(D_alpha_used, D_alpha_new, oda_step.lam) _oda_mix(D_beta_used, D_beta_new, oda_step.lam) D_alpha_prev = D_alpha_real D_beta_prev = D_beta_real D_alpha_real = D_alpha_used D_beta_real = D_beta_used density_from_c_per_k = oda_step.lam == 1.0 plog.info( f" ODA: lambda = {oda_step.lam:.4f} " f"(g0 = {oda_step.g0:+.3e}, g1 = {oda_step.g1:+.3e})" ) else: D_alpha_prev = D_alpha_used D_beta_prev = D_beta_used D_alpha_real = D_alpha_new D_beta_real = D_beta_new density_from_c_per_k = True # Snapshot for next iter MOM (use_mom: every cycle; PATTERN_HOLD: while # inside the hold window, so cycle k+1 can hold against cycle k). if use_mom or (_spinlock_pattern_hold and iter_idx <= _spinlock_iters): C_prev_occ_alpha_per_k = [ np.asarray(C_alpha_per_k[idx][:, :n_alpha]).copy() if n_alpha > 0 else np.zeros((C_alpha_per_k[idx].shape[0], 0), dtype=complex) for idx in range(n_k) ] C_prev_occ_beta_per_k = [ np.asarray(C_beta_per_k[idx][:, :n_beta]).copy() if n_beta > 0 else np.zeros((C_beta_per_k[idx].shape[0], 0), dtype=complex) for idx in range(n_k) ] if damper is not None: damper.update(free_energy) E_prev = free_energy if converged: break if n_alpha == 0 or n_beta == 0: s2 = 0.25 * (n_alpha - n_beta) * (n_alpha - n_beta + 2) + n_beta else: k0_idx = 0 for idx, k in enumerate(k_points): if np.allclose(np.asarray(k, dtype=float), 0.0): k0_idx = idx break s2 = _spin_squared( n_alpha, n_beta, np.real(C_alpha_per_k[k0_idx]), np.real(C_beta_per_k[k0_idx]), np.real(S_k_list[k0_idx]), ) plog.converged(n_iter=iter_idx, energy=E_total, converged=converged) # ---- Ionic-Gamma basin-health diagnostic (smearing straddle, per spin) - # See run_pbc_bipole_rks / smearing_basin_warning. Both spin channels # are checked; the minimum per-k gap across spins governs the trigger. basin_warning = smearing_basin_warning( smearing_T, [ (eps_alpha_per_k, occ_alpha_per_k, n_alpha, 1.0), (eps_beta_per_k, occ_beta_per_k, n_beta, 1.0), ], entropy, "run_pbc_bipole_uhf", ) if basin_warning is not None: plog.info(" WARNING: " + basin_warning) warnings.warn(basin_warning, UserWarning, stacklevel=2) # ---- Post-loop: recompute energy on final density for consistency if converged: _fb = _build_fock_for_density( D_alpha_real, D_beta_real, coeffs_alpha_for_rho=C_alpha_per_k, coeffs_beta_for_rho=C_beta_per_k, use_incremental=False, ) D_tot = _combine_density_sets( basis, system, lat_opts_2e, D_alpha_real, D_beta_real ) E_kin_final = _lattice_contract(D_tot, T_lat, operator_name="T") E_ne_final = _lattice_contract(D_tot, V_lat, operator_name="V_ne") E_2e_final = _fb.e_2e_k_correction + 0.5 * ( _lattice_contract(D_alpha_real, _fb.f2e_alpha_real, operator_name="F2e") + _lattice_contract(D_beta_real, _fb.f2e_beta_real, operator_name="F2e") ) E_elec = E_kin_final + E_ne_final + E_2e_final E_total = float(E_elec) + e_nuc + e_dft_plus_u # Fresh E_total doesn't include spheropole -- add it (3D only; # zero in the direct dim<3 gauge, omitted under the corrected # gauge). if system.dim == 3 and not exchange_split_active: E_sphero_final = compute_ext_el_spheropole(D_tot, basis, system, lat_opts) E_total += E_sphero_final else: E_sphero_final = None else: E_sphero_final = energy_components[-1].e_ext_el_spheropole free_energy_final = E_total - smearing_T * entropy return PBCBipoleUHFResult( energy=float(E_total), e_electronic=float(E_elec), e_nuclear=e_nuc, e_ext_el_spheropole=E_sphero_final, 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, ewald_alpha_bohr_inv=omega_used, e_dft_plus_u=float(e_dft_plus_u), energy_components=energy_components, exchange_ewald_split=bool(exchange_split_active), exchange_exxdiv=(exchange_exxdiv if exchange_split_active else None), basin_warning=basin_warning, smearing_temperature=smearing_T, fermi_level=float(mu_alpha) if n_alpha > 0 else float(mu_beta), entropy=float(entropy), free_energy=float(free_energy_final), occupations_alpha=[np.asarray(o, dtype=float) for o in occ_alpha_per_k], occupations_beta=[np.asarray(o, dtype=float) for o in occ_beta_per_k], kpoints_cart=np.asarray(k_points, dtype=float).reshape(-1, 3), kpoint_weights=np.asarray(weights, dtype=float).reshape(-1), )