{"schema_version":1,"experiment_id":"eoa_inverse_innovation_exp09_archetype_breadth150_20260804","cell_id":"constraint_propagation_and_decoupling__chemistry_materials","arm":"BREADTH_PROBE_ONE_SHOT","candidate_id":"constraint_propagation_and_decoupling__chemistry_materials__P1","proposal_index":1,"version":0,"title":"Charge-Neutrality-First Partitioning of Doped Perovskite Synthesis","problem":"A solid-state chemistry team is developing an aliovalently doped perovskite oxide represented as A1-xDxBO3-δ. Nominal dopant fraction, allowed lattice sites, cation valences, oxygen-vacancy concentration, firing atmosphere, temperature, and competing-phase limits are treated as loosely coordinated choices. Recipes that appear locally reasonable can therefore imply impossible charge compensation, exceed site occupancy, or require an oxygen chemical potential incompatible with the selected firing schedule.","actors":["Solid-state chemist defining the target composition","Materials modeler maintaining defect and phase constraints","Laboratory technician batching and firing powders","Diffraction analyst assessing phase assemblage","Laboratory lead responsible for process and safety approval"],"observable_state":"Recipe records use inconsistent formula normalizations and independently selected dopant levels and firing atmospheres; some fired specimens show unplanned diffraction peaks, mass changes inconsistent with the assumed oxygen deficiency, or nominally identical compositions that cannot be compared because their implied charge-compensation states differ.","consequence":"The team cannot tell whether a failed specimen reflects an infeasible nominal composition, an incompatible atmosphere, or a local synthesis failure. It may repeat chemically inconsistent recipes or attribute measured properties to dopant identity when oxygen stoichiometry or secondary phases changed simultaneously.","affected_objective":"Define and synthesize a composition-and-processing specification whose cation balance, charge neutrality, site occupancy, oxygen-stoichiometry bounds, phase restrictions, and furnace limits remain mutually consistent and whose bulk-composition and atmosphere work can be assigned with explicit interface conditions.","intervention":"Build a constraint network connecting cation fractions, possible site assignments and valences, δ, charge-compensation modes, oxygen chemical potential, firing temperature, competing phases, and furnace capabilities. Normalize every candidate to one ABO3-δ formula unit, propagate mass-balance and charge-neutrality implications to eliminate impossible or equivalent candidates, and record minimal conflicting constraint sets. Use separator analysis to determine whether cation batching and atmosphere scheduling can be solved as separate subproblems linked by an allowable δ range, oxygen-chemical-potential window, and temperature interval. Recombine each local proposal and test it against the original constraints before authorizing synthesis.","structural_mapping":[{"archetype_element":"Constraint Network Model","domain_realization":"A bipartite network whose variable nodes include A-, D-, and B-site fractions, oxidation states, δ, firing temperature, oxygen partial pressure, and phase labels, and whose constraint nodes include elemental balance, charge neutrality, site occupancy, phase exclusions, and furnace operating limits."},{"archetype_element":"Implication propagation","domain_realization":"A proposed dopant fraction and site assignment propagate through charge neutrality to allowable combinations of B-site valence and oxygen vacancies; these bounds then propagate to permissible firing atmospheres and phase fields."},{"archetype_element":"Redundancy elimination","domain_realization":"All formulas are expressed per one ABO3-δ unit so scalar multiples and alternative bookkeeping conventions do not consume separate search or review effort."},{"archetype_element":"Coupling Boundary Map","domain_realization":"Cation batching variables and furnace-control variables are considered separable only where their remaining connection is captured by an explicit δ, oxygen-chemical-potential, and temperature interface contract."},{"archetype_element":"Decoupled Subproblem Partition","domain_realization":"One subproblem selects feasible cation ratios and compensation modes; another selects a realizable atmosphere-temperature schedule within the derived interface window."},{"archetype_element":"Consistency and Recomposition Check","domain_realization":"The chosen recipe and firing schedule are recombined, charge and mass balances are recalculated, and predicted phase and oxygen-stoichiometry bounds are checked before laboratory release."}],"mechanism_mapping":[{"mechanism_slug":"constraint_dependency_matrix","role":"Shows which compositional, defect-chemical, phase, and furnace constraints can alter each variable and makes propagation paths auditable.","counterfactual_removal":"Without the matrix, atmosphere and composition dependencies remain implicit, so a proposed partition cannot be justified."},{"mechanism_slug":"domain_reduction_pass","role":"Applies elemental balance, site capacity, allowed valence, charge neutrality, and equipment bounds until each candidate domain is narrowed or declared contradictory.","counterfactual_removal":"Without reduction, teams continue evaluating recipes already excluded by basic chemical or equipment constraints."},{"mechanism_slug":"gauge_fixing_choice","role":"Fixes one ABO3-δ formula-unit normalization while preserving elemental ratios and charge-relevant observables.","counterfactual_removal":"Without normalization, equivalent formula representations can be mistaken for distinct compositions and their δ values can be compared incorrectly."},{"mechanism_slug":"cut_set_or_separator_analysis","role":"Tests whether δ, oxygen chemical potential, and temperature form a sufficient interface between cation-recipe and furnace-schedule decisions.","counterfactual_removal":"Without separator analysis, the work may be split organizationally despite hidden cross-boundary chemical dependencies."},{"mechanism_slug":"recomposition_consistency_test","role":"Rejoins the selected recipe and schedule and verifies the original balance, occupancy, phase, and equipment constraints.","counterfactual_removal":"Without recomposition, locally feasible outputs can reach the furnace as a globally inconsistent synthesis specification."}],"causal_chain":["Inconsistent formula conventions and unpropagated defect-chemical constraints make composition and firing variables appear independently selectable.","Formula-unit normalization removes representational duplicates without changing elemental ratios or charge observables.","Mass balance, site occupancy, and charge neutrality propagate a proposed dopant choice into bounds on oxidation states and δ.","Those derived bounds exclude compensation modes and atmosphere-temperature combinations that cannot coexist with the proposal.","Separator analysis identifies whether the remaining composition-process coupling can be expressed as a bounded interface contract.","The composition and furnace subproblems are solved locally under that shared contract.","Recomposition exposes any residual violation before synthesis, leaving either a globally consistent specification or an explicit conflict requiring constraint review."],"baseline":"The baseline is spreadsheet-based recipe selection in which a chemist chooses nominal dopant levels, a technician applies a familiar firing schedule, and inconsistencies are discovered after synthesis through diffraction, mass-change, or property measurements. Constraints may be checked individually, but their implications are not systematically propagated before the work is divided.","nearest_rivals":["A factorial design of experiments that samples dopant level and firing atmosphere without first eliminating chemically infeasible combinations","One-factor-at-a-time recipe adjustment following each unsuccessful firing","Thermodynamic phase screening that predicts candidate stability but does not partition operational decisions with explicit interface conditions","A black-box composition optimizer that proposes candidates without an inspectable implication register or recomposition test"],"remaining_contrastive_claim":"The distinguishing claim is procedural: composition and firing decisions are separated only after balance, charge, occupancy, phase, and equipment implications have reduced the domain and exposed a sufficient residual interface. Unlike direct experimental search or standalone phase screening, every local proposal must recompose into a specification satisfying the original declared constraints.","authority_safety":{"decision_authority":"The laboratory lead owns constraint classification and synthesis release; the responsible chemist may propose compositions, while furnace-operation and gas-handling limits remain under the laboratory's designated safety authority.","authorized_first_step":"Conduct a read-only audit of up to eight existing recipe-and-outcome records using one declared host lattice and dopant family; normalize formulas, propagate the recorded constraints, and compare predicted feasibility classes with already available diffraction and mass-change observations.","excluded_actions":["Starting a new synthesis","Changing furnace temperature, pressure, or gas composition","Introducing a new precursor or dopant","Relaxing a hard chemical or equipment constraint without laboratory-lead approval","Treating a model-derived oxidation state or δ value as a measured result"],"halt_rollback":"Stop the audit if precursor identities, nominal compositions, atmosphere records, or measurement labels cannot be reconciled without guessing. Preserve the original records unchanged, discard derived partitions dependent on the disputed fields, and return to the baseline review process until the laboratory lead resolves them."},"negative_tests":{"strongest_counterevidence":"Existing outcomes may be governed mainly by milling history, contamination, kinetic trapping, volatilization, or measurement error absent from the constraint network, while charge-neutrality and phase-feasibility constraints already hold across both successful and unsuccessful specimens.","problem_falsifier":"The inferred coupling problem is falsified if normalized historical records show no contradictions, equivalent representations, or constraint-derived exclusions and each outcome can be explained by a single already-isolated local process variable.","intervention_falsifier":"The intervention is falsified for this use if prospectively hidden historical outcomes do not align with the reduced feasible and infeasible classes, or if recipe and furnace proposals satisfying the derived interface repeatedly fail the recomposition check because material cross-dependencies cannot be bounded by that interface.","risks":["Incorrect valence or site-occupancy assumptions can prune feasible chemistry.","A normalization choice may conceal volatilization or nonstoichiometric cation loss if those variables are omitted.","Equilibrium phase constraints may be misapplied to kinetically trapped synthesis outcomes.","Treating soft phase preferences as hard exclusions can overconstrain the candidate set.","Approximate composition-process decoupling may hide residual dependencies involving heating rate, dwell time, precursor morphology, or gas transport.","An apparently consistent paper specification may be mistaken for evidence of phase purity or material performance."]},"next_evidence_step":"Blind the diffraction and mass-change outcome labels for the same maximum of eight existing records, have the team classify each normalized recipe as feasible, contradictory, or indeterminate using the constraint network, then reveal the labels and document every agreement, disagreement, missing constraint, and failed partition. Do not expand the model or authorize synthesis within this step.","prior_art_status":"UNSEARCHED","diversity_from_prior_proposals":"Not assessed against prior proposals because runtime isolation prohibits inspecting them; the candidate is derived solely from the supplied archetype and chemistry/materials domain card and centers defect-chemical constraints in aliovalently doped perovskite synthesis.","revision_record":{"parent_version":null,"progress_targets_addressed":["Initial one-shot proposal generated from the supplied archetype and domain card"],"conceptual_changes":[],"operational_changes":[],"evidence_changes":[],"claim_changes":[]}}