Source code for vibeqc.periodic_uks_ewald

"""Phase 15c-3a: Γ-point periodic UKS SCF driver using the composed
EWALD_3D Coulomb dispatch.

Open-shell DFT counterpart of :func:`run_rks_periodic_gamma_ewald3d`
(15c-1) and :func:`run_uhf_periodic_gamma_ewald3d` (15a). Per SCF
iteration:

    F_α  =  H_core  +  J_ewald(ω, D_α + D_β)  −  α·K(D_α)  +  V_xc^α
    F_β  =  H_core  +  J_ewald(ω, D_α + D_β)  −  α·K(D_β)  +  V_xc^β

where ``α = func.hf_exchange_fraction``. Compared to UHF Ewald (15a)
which uses ``-K_σ`` (full HF exchange per spin), here we scale by α
for hybrids and skip K entirely for pure DFT.

V_xc comes from the new :func:`build_xc_periodic_uks` (Phase 15c-3
C++ addition), which returns separate V_α / V_β / E_xc from
spin-resolved densities. The functional is constructed with
``spin=2`` to take the libxc polarized path.

Density flow.  Γ-only molecular-limit cells have all electron density
in the home cell, so per-spin densities are wrapped in degenerate
LatticeMatrixSets (block 0 = D_σ, others zero) before being handed
to ``build_xc_periodic_uks``. Same trick as the Γ-only RKS Ewald
driver — exact in the molecular limit, the regime ``build_j_ewald_3d``
itself targets at Γ.

Energy formula. From the molecular UKS pattern (uks.cpp):

    E_elec  =  E_xc  +  tr((D_α + D_β)·H_core)
                     +  ½ tr(D_α·F_HF_α) + ½ tr(D_β·F_HF_β)

where ``F_HF_σ = J(D_total) − α·K(D_σ)`` is the HF-exchange piece
of F_σ (V_xc reported through E_xc rather than a trace).

Scope.

  * Γ-only single k-point.
  * Open-shell, ``multiplicity ≥ 1``.
  * Pure DFT, hybrid, and HF (``α = 1``, equivalent to UHF Ewald).
  * DIIS on the block-diagonal [α, β] error vector with one rolling
    history per spin (matches UHF Ewald and the molecular UKS C++
    driver's convention).
  * Saunders-Hillier level shift via ``options.level_shift``.
  * Periodic Becke partition selectable via
    ``options.use_periodic_becke``.

The multi-k UKS Ewald driver lands in
:mod:`vibeqc.periodic_uks_multi_k_ewald` (15c-3b); it shares the
helpers with :mod:`vibeqc.periodic_uhf_multi_k_ewald` and adds the
periodic UKS XC.
"""

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,
    CoulombMethod,
    Functional,
    InitialGuess,
    LatticeMatrixSet,
    LatticeSumOptions,
    PeriodicKSOptions,
    PeriodicSystem,
    SCFIteration,
    bloch_sum,
    build_grid,
    build_jk_gamma_molecular_limit,
    build_xc_periodic_uks,
    compute_kinetic_lattice,
    compute_nuclear_lattice,
    compute_overlap_lattice,
    nuclear_repulsion_per_cell,
)
from .ewald_composed import build_j_ewald_3d
from .ewald_j import auto_grid
from .guess import initial_densities_open_shell
from .madelung import (
    madelung_energy_correction_for_lat as _madelung_energy_correction_for_lat,
)
from .periodic_grid import build_periodic_becke_grid
from .periodic_rhf_ewald import _canonical_orthogonalizer
from .periodic_scf_accelerators import DynamicDamping, PeriodicSCFAccelerator
from .periodic_uhf_ewald import _spin_squared
from .progress import ProgressLogger, resolve_progress
from .scf_divergence import check_scf_divergence

__all__ = [
    "PeriodicUKSEwaldResult",
    "run_uks_periodic_gamma_ewald3d",
]


[docs] @dataclass class PeriodicUKSEwaldResult: """Result of :func:`run_uks_periodic_gamma_ewald3d`. Spin-resolved counterpart of :class:`PeriodicRKSEwaldResult` with UHF-style ``s_squared`` diagnostic. All matrices are at Γ. """ energy: float e_electronic: float e_nuclear: float e_xc: float e_coulomb: float e_hf_exchange: float n_iter: int converged: bool s_squared: float s_squared_ideal: float # α spin mo_energies_alpha: np.ndarray mo_coeffs_alpha: np.ndarray density_alpha: np.ndarray fock_alpha: np.ndarray # β spin mo_energies_beta: np.ndarray mo_coeffs_beta: np.ndarray density_beta: np.ndarray fock_beta: np.ndarray overlap: np.ndarray functional: str = "" scf_trace: List[SCFIteration] = field(default_factory=list) omega: float = 0.0 grid_shape: Tuple[int, int, int] = (0, 0, 0)
def _density_set_gamma( template: LatticeMatrixSet, D: np.ndarray, ) -> LatticeMatrixSet: """Wrap the Γ-folded density ``D`` in a degenerate :class:`LatticeMatrixSet` matching the cell layout of ``template``: block 0 = D, every other block = zeros. Mutates ``template`` in place (LatticeMatrixSet's ``.blocks`` list is a transient copy; real mutation goes through ``set_block``).""" n_bf = D.shape[0] if n_bf != template.nbf: raise ValueError( f"_density_set_gamma: D has nbf={n_bf} but template has nbf={template.nbf}" ) zero = np.zeros_like(D) for i in range(len(template)): template.set_block(i, D if i == 0 else zero) return template
[docs] def run_uks_periodic_gamma_ewald3d( system: PeriodicSystem, basis: BasisSet, options: Optional[PeriodicKSOptions] = 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, ) -> PeriodicUKSEwaldResult: """Γ-point open-shell periodic Kohn-Sham SCF with Ewald-3D Coulomb. Parameters mirror :func:`run_rks_periodic_gamma_ewald3d`. Multiplicity is read from ``system.multiplicity``; the driver handles closed-shell (mult=1, special case where α=β occupation) and open-shell systems uniformly. Returns ------- :class:`PeriodicUKSEwaldResult`. """ opts = options if options is not None else PeriodicKSOptions() lat_opts = 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 the jellium # background terms cancel exactly. Mirrors the override block in # run_rks_periodic_gamma_ewald3d (commit 49f8ae91). The driver # kwarg ``omega`` is retained for signature parity but overridden # here; users override via ``opts.ewald_omega`` when needed. _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"UKS Gamma EWALD_3D / functional={opts.functional!r}, " f"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, [ ("PeriodicKSOptions", 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)) n_elec = system.n_electrons() mult = int(system.multiplicity) if mult < 1: raise ValueError( f"run_uks_periodic_gamma_ewald3d: multiplicity must be ≥ 1; got {mult}" ) n_alpha = (n_elec + mult - 1) // 2 n_beta = (n_elec - mult + 1) // 2 if n_alpha + n_beta != n_elec: raise ValueError( "run_uks_periodic_gamma_ewald3d: n_electrons and multiplicity " f"are inconsistent (n_e={n_elec}, mult={mult})" ) if n_beta < 0: raise ValueError( f"run_uks_periodic_gamma_ewald3d: n_beta < 0; n_e={n_elec}, mult={mult}" ) # ---- Functional + DFT grid ------------------------------------------ func = Functional(opts.functional, 2) # spin-polarized alpha = float(func.hf_exchange_fraction) if opts.use_periodic_becke: grid = build_periodic_becke_grid( system, grid_options=opts.grid, image_radius_bohr=float(opts.becke_image_radius_bohr), ) else: grid = build_grid(system.unit_cell_molecule(), opts.grid) plog.info( f"UKS Gamma occupations: n_alpha = {n_alpha}, " f"n_beta = {n_beta} (multiplicity = {mult})" ) # ---- 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, ) opt_rep = optimize_truncation(system, basis, lattice_opts=lat_opts) 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; SCF will run " "with the last evaluated settings." ) lat_opts = opt_rep.optimized_lattice_opts # ---- One-electron integrals at Γ ------------------------------------ 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) k_gamma = np.zeros(3) S = np.real(bloch_sum(S_lat, k_gamma)) T = np.real(bloch_sum(T_lat, k_gamma)) V = np.real(bloch_sum(V_lat, k_gamma)) Hcore = T + V S = 0.5 * (S + S.T) Hcore = 0.5 * (Hcore + Hcore.T) # Linear-dependence preflight on S(Γ); see periodic_rhf_ewald.py. from .linear_dependence import scf_preflight_overlap_check scf_preflight_overlap_check( S, plog=plog, label="S(Γ)", basis=basis, ) X, n_kept = _canonical_orthogonalizer( S, linear_dep_threshold, normalize_diag_first=canonical_orth_normalize_diag_first, ) if max(n_alpha, n_beta) > n_kept: raise RuntimeError( "run_uks_periodic_gamma_ewald3d: canonical orthogonalisation " f"kept {n_kept} directions; need ≥ {max(n_alpha, n_beta)} " f"(n_α={n_alpha}, n_β={n_beta})." ) e_nuc = float(nuclear_repulsion_per_cell(system, lat_opts)) def diagonalise(F: np.ndarray) -> Tuple[np.ndarray, np.ndarray]: Fp = X.T @ F @ X Fp = 0.5 * (Fp + Fp.T) eps, Cp = np.linalg.eigh(Fp) return X @ Cp, eps # ---- Initial guess via the unified engine. # Bug fix (v0.9.x): this Γ-only UKS path previously ignored # ``opts.initial_guess`` and always used HCore. The engine call # respects the request; HCore reproduces the prior behaviour. guess = getattr(opts, "initial_guess", InitialGuess.HCORE) # Seed the per-spin MO frame from Hcore for the quadratic-step # tracking (used even when SAD provides the start density). C_alpha, eps_alpha = diagonalise(Hcore) C_beta, eps_beta = diagonalise(Hcore) split = initial_densities_open_shell( system.unit_cell_molecule(), basis, n_alpha, n_beta, guess, is_periodic=True, ) if split is not None: D_alpha, D_beta = split else: D_alpha = ( C_alpha[:, :n_alpha] @ C_alpha[:, :n_alpha].T if n_alpha > 0 else np.zeros_like(Hcore) ) D_beta = ( C_beta[:, :n_beta] @ C_beta[:, :n_beta].T if n_beta > 0 else np.zeros_like(Hcore) ) D_alpha = 0.5 * (D_alpha + D_alpha.T) D_beta = 0.5 * (D_beta + D_beta.T) D_alpha_prev = D_alpha.copy() D_beta_prev = D_beta.copy() damping = float(opts.damping) if not (0.0 <= damping < 1.0): raise ValueError( f"run_uks_periodic_gamma_ewald3d: 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[PeriodicSCFAccelerator] = ( PeriodicSCFAccelerator(opts) if use_diis else None ) level_shift = float(getattr(opts, "level_shift", 0.0)) # Phase C1c — quadratic SCF fallback (per-spin 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) ) # Track per-spin MO basis between iterations for the C1c step. C_alpha_prev_mo = C_alpha eps_alpha_prev_mo = eps_alpha C_beta_prev_mo = C_beta eps_beta_prev_mo = eps_beta # Pre-allocate degenerate LMS templates for D_α and D_β (V_xc input). D_alpha_set = compute_overlap_lattice(basis, system, lat_opts) D_beta_set = compute_overlap_lattice(basis, system, lat_opts) # ---- SCF loop ------------------------------------------------------- scf_trace: List[SCFIteration] = [] s_squared_ideal = 0.25 * (mult - 1) * (mult + 1) result = PeriodicUKSEwaldResult( energy=0.0, e_electronic=0.0, e_nuclear=e_nuc, e_xc=0.0, e_coulomb=0.0, e_hf_exchange=0.0, n_iter=0, converged=False, s_squared=0.0, s_squared_ideal=s_squared_ideal, mo_energies_alpha=np.empty(0), mo_coeffs_alpha=np.empty((0, 0)), density_alpha=D_alpha.copy(), fock_alpha=np.empty((0, 0)), mo_energies_beta=np.empty(0), mo_coeffs_beta=np.empty((0, 0)), density_beta=D_beta.copy(), fock_beta=np.empty((0, 0)), overlap=S, functional=str(opts.functional), scf_trace=scf_trace, omega=float(omega), grid_shape=grid_shape_t, ) E_prev = 0.0 plog.banner(f"SCF (UKS Gamma {opts.functional!r}, EWALD_3D)") plog.info(" iter energy (Ha) dE ||[F,DS]|| DIIS") 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 if iter_idx == 1 or damping == 0.0 or diis_active: D_alpha_used = D_alpha D_beta_used = D_beta else: D_alpha_used = damping * D_alpha_prev + (1.0 - damping) * D_alpha D_beta_used = damping * D_beta_prev + (1.0 - damping) * D_beta D_total = D_alpha_used + D_beta_used # Hartree J via Ewald — same convention as UHF Ewald. J = build_j_ewald_3d( basis, system, D_total, omega=float(omega), lattice_opts=lat_opts, grid_shape=grid_shape_t, origin=origin, spacing_bohr=spacing_bohr, ) # Per-spin K (only when α > 0 — pure DFT skips this). if alpha != 0.0: jk_alpha = build_jk_gamma_molecular_limit( basis, system, lat_opts, 2.0 * D_alpha_used, 0.0, ) jk_beta = build_jk_gamma_molecular_limit( basis, system, lat_opts, 2.0 * D_beta_used, 0.0, ) # K(D_σ) = K(2·D_σ) / 2 (RHF convention inside the builder). K_alpha = 0.5 * np.asarray(jk_alpha.K) K_beta = 0.5 * np.asarray(jk_beta.K) else: K_alpha = None K_beta = None # V_xc via the periodic UKS XC kernel. _density_set_gamma(D_alpha_set, D_alpha_used) _density_set_gamma(D_beta_set, D_beta_used) xc = build_xc_periodic_uks( basis, system, grid, func, D_alpha_set, D_beta_set, lat_opts, ) V_xc_alpha = np.real(bloch_sum(xc.V_alpha, k_gamma)) V_xc_beta = np.real(bloch_sum(xc.V_beta, k_gamma)) V_xc_alpha = 0.5 * (V_xc_alpha + V_xc_alpha.T) V_xc_beta = 0.5 * (V_xc_beta + V_xc_beta.T) E_xc = float(xc.e_xc) # F_σ = Hcore + J − α·K_σ + V_xc^σ if K_alpha is not None: F_HF_alpha = J - alpha * K_alpha F_HF_beta = J - alpha * K_beta else: F_HF_alpha = J F_HF_beta = J F_alpha = Hcore + F_HF_alpha + V_xc_alpha F_beta = Hcore + F_HF_beta + V_xc_beta F_alpha = 0.5 * (F_alpha + F_alpha.T) F_beta = 0.5 * (F_beta + F_beta.T) # Energy decomposition. E_core_trace = float(np.einsum("ij,ij->", D_total, Hcore)) E_HF_alpha_trace = 0.5 * float(np.einsum("ij,ij->", D_alpha_used, F_HF_alpha)) E_HF_beta_trace = 0.5 * float(np.einsum("ij,ij->", D_beta_used, F_HF_beta)) E_elec = E_xc + E_core_trace + E_HF_alpha_trace + E_HF_beta_trace # Madelung-leak correction (v0.6.1). E_madelung_fix = _madelung_energy_correction_for_lat( D_alpha_used + D_beta_used, S, system, lat_opts ) E_total = E_elec + e_nuc + E_madelung_fix # Reporting decomposition: J vs HF-K. E_coulomb = 0.5 * float(np.einsum("ij,ij->", D_total, J)) if K_alpha is not None: E_hf_K = -0.5 * alpha * float( np.einsum("ij,ij->", D_alpha_used, K_alpha) ) - 0.5 * alpha * float(np.einsum("ij,ij->", D_beta_used, K_beta)) else: E_hf_K = 0.0 # Per-spin orbital-gradient norms. FDS_alpha = F_alpha @ D_alpha_used @ S FDS_beta = F_beta @ D_beta_used @ S grad_alpha = FDS_alpha - FDS_alpha.T grad_beta = FDS_beta - FDS_beta.T grad_norm = float( np.sqrt(np.linalg.norm(grad_alpha) ** 2 + np.linalg.norm(grad_beta) ** 2) ) dE = E_total - E_prev # Divergence detection (v0.6.2). check_scf_divergence( "run_uks_periodic_gamma_ewald3d", iter_idx, E_total, grad_norm, 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), 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), diis=diis_sub, ) # Per-iter energy decomposition for cross-code parity comparison. E_kin_iter = float(np.einsum("ij,ij->", D_total, T)) E_ne_iter = float(np.einsum("ij,ij->", D_total, V)) plog.energy_decomposition( iter_idx, E_kin=E_kin_iter, E_ne=E_ne_iter, E_J=E_coulomb, E_xc=float(E_xc), E_K=float(E_hf_K), E_nuc=float(e_nuc), E_madelung=float(E_madelung_fix), ) converged = ( iter_idx > 1 and abs(dE) < float(opts.conv_tol_energy) and grad_norm < float(opts.conv_tol_grad) ) # Phase C1c gate. in_quadratic_phase = ( quadratic_fallback_iter > 0 and iter_idx > quadratic_fallback_iter ) if in_quadratic_phase: from .quadratic_scf import quadratic_step C_alpha_new, eps_alpha_new = quadratic_step( F_alpha, C_alpha_prev_mo, eps_alpha_prev_mo, n_alpha, shift=quadratic_fallback_shift, max_step=quadratic_fallback_max_step, ) C_beta_new, eps_beta_new = quadratic_step( F_beta, C_beta_prev_mo, eps_beta_prev_mo, n_beta, shift=quadratic_fallback_shift, max_step=quadratic_fallback_max_step, ) else: # SCF-accelerator extrapolation (DIIS per-spin Pulay, # KDIIS / EDIIS / ADIIS spin-coupled — matches the C++ # UHF dispatch). if accel is not None: F_alpha_ex, F_beta_ex = accel.extrapolate_uhf( F_alpha, F_beta, error_alpha=grad_alpha, error_beta=grad_beta, density_alpha=D_alpha_used, density_beta=D_beta_used, energy=E_total, mo_coeffs_alpha=C_alpha_prev_mo, mo_coeffs_beta=C_beta_prev_mo, mo_energies_alpha=eps_alpha_prev_mo, mo_energies_beta=eps_beta_prev_mo, n_alpha=n_alpha, n_beta=n_beta, ) if diis_active: F_alpha = F_alpha_ex F_beta = F_beta_ex # Saunders-Hillier level shift per spin. if level_shift != 0.0: F_alpha_diag = ( F_alpha + level_shift * S - (level_shift / 2.0) * (S @ D_alpha_used @ S) ) F_beta_diag = ( F_beta + level_shift * S - (level_shift / 2.0) * (S @ D_beta_used @ S) ) F_alpha_diag = 0.5 * (F_alpha_diag + F_alpha_diag.T) F_beta_diag = 0.5 * (F_beta_diag + F_beta_diag.T) else: F_alpha_diag = F_alpha F_beta_diag = F_beta C_alpha_new, eps_alpha_new = diagonalise(F_alpha_diag) C_beta_new, eps_beta_new = diagonalise(F_beta_diag) C_alpha_prev_mo = C_alpha_new eps_alpha_prev_mo = eps_alpha_new C_beta_prev_mo = C_beta_new eps_beta_prev_mo = eps_beta_new D_alpha_prev = D_alpha_used D_beta_prev = D_beta_used D_alpha = ( C_alpha_new[:, :n_alpha] @ C_alpha_new[:, :n_alpha].T if n_alpha > 0 else np.zeros_like(Hcore) ) D_beta = ( C_beta_new[:, :n_beta] @ C_beta_new[:, :n_beta].T if n_beta > 0 else np.zeros_like(Hcore) ) D_alpha = 0.5 * (D_alpha + D_alpha.T) D_beta = 0.5 * (D_beta + D_beta.T) result.energy = E_total result.e_electronic = E_elec result.e_xc = E_xc result.e_coulomb = E_coulomb result.e_hf_exchange = E_hf_K result.n_iter = iter_idx result.mo_energies_alpha = eps_alpha_new result.mo_coeffs_alpha = C_alpha_new result.density_alpha = D_alpha_used result.fock_alpha = F_alpha result.mo_energies_beta = eps_beta_new result.mo_coeffs_beta = C_beta_new result.density_beta = D_beta_used result.fock_beta = F_beta if damper is not None: damper.update(E_total) E_prev = E_total if converged: # Final consistency pass on the fresh densities. D_total_f = D_alpha + D_beta J_f = build_j_ewald_3d( basis, system, D_total_f, omega=float(omega), lattice_opts=lat_opts, grid_shape=grid_shape_t, origin=origin, spacing_bohr=spacing_bohr, ) if alpha != 0.0: jk_a_f = build_jk_gamma_molecular_limit( basis, system, lat_opts, 2.0 * D_alpha, 0.0, ) jk_b_f = build_jk_gamma_molecular_limit( basis, system, lat_opts, 2.0 * D_beta, 0.0, ) K_alpha_f = 0.5 * np.asarray(jk_a_f.K) K_beta_f = 0.5 * np.asarray(jk_b_f.K) else: K_alpha_f = None K_beta_f = None _density_set_gamma(D_alpha_set, D_alpha) _density_set_gamma(D_beta_set, D_beta) xc_f = build_xc_periodic_uks( basis, system, grid, func, D_alpha_set, D_beta_set, lat_opts, ) V_xc_a_f = np.real(bloch_sum(xc_f.V_alpha, k_gamma)) V_xc_b_f = np.real(bloch_sum(xc_f.V_beta, k_gamma)) V_xc_a_f = 0.5 * (V_xc_a_f + V_xc_a_f.T) V_xc_b_f = 0.5 * (V_xc_b_f + V_xc_b_f.T) E_xc_f = float(xc_f.e_xc) if K_alpha_f is not None: F_HF_a_f = J_f - alpha * K_alpha_f F_HF_b_f = J_f - alpha * K_beta_f else: F_HF_a_f = J_f F_HF_b_f = J_f F_alpha_f = Hcore + F_HF_a_f + V_xc_a_f F_beta_f = Hcore + F_HF_b_f + V_xc_b_f F_alpha_f = 0.5 * (F_alpha_f + F_alpha_f.T) F_beta_f = 0.5 * (F_beta_f + F_beta_f.T) C_a_f, eps_a_f = diagonalise(F_alpha_f) C_b_f, eps_b_f = diagonalise(F_beta_f) E_core_f = float(np.einsum("ij,ij->", D_alpha + D_beta, Hcore)) E_HF_a_f = 0.5 * float(np.einsum("ij,ij->", D_alpha, F_HF_a_f)) E_HF_b_f = 0.5 * float(np.einsum("ij,ij->", D_beta, F_HF_b_f)) E_elec_f = E_xc_f + E_core_f + E_HF_a_f + E_HF_b_f E_coulomb_f = 0.5 * float(np.einsum("ij,ij->", D_alpha + D_beta, J_f)) if K_alpha_f is not None: E_hf_K_f = -0.5 * alpha * float( np.einsum("ij,ij->", D_alpha, K_alpha_f) ) - 0.5 * alpha * float(np.einsum("ij,ij->", D_beta, K_beta_f)) else: E_hf_K_f = 0.0 E_madelung_fix_f = _madelung_energy_correction_for_lat( D_alpha + D_beta, S, system, lat_opts ) result.energy = E_elec_f + e_nuc + E_madelung_fix_f result.e_electronic = E_elec_f result.e_xc = E_xc_f result.e_coulomb = E_coulomb_f result.e_hf_exchange = E_hf_K_f result.mo_energies_alpha = eps_a_f result.mo_coeffs_alpha = C_a_f result.density_alpha = D_alpha result.fock_alpha = F_alpha_f result.mo_energies_beta = eps_b_f result.mo_coeffs_beta = C_b_f result.density_beta = D_beta result.fock_beta = F_beta_f result.s_squared = _spin_squared( n_alpha, n_beta, C_a_f, C_b_f, S, ) result.converged = True plog.converged( n_iter=result.n_iter, energy=result.energy, converged=True, ) return result # Did not converge — populate ⟨S²⟩ on the final iterate. result.s_squared = _spin_squared( n_alpha, n_beta, result.mo_coeffs_alpha, result.mo_coeffs_beta, S, ) plog.converged( n_iter=result.n_iter, energy=result.energy, converged=False, ) return result