{
  "abstract": "Identical time-resolved and steady-state optical observables can correspond to different reaction quantum yields when reactive and non-reactive dark exits are not independently resolved. We formulate linear photochemical networks as stable input-output systems with kinetic matrix K, observation matrix B, and reaction output vector q. Complete integrated yields are Φobs = BRu and ΦR = q⊤Ru, where R = (−K)−1 is the cumulative residence-time matrix. Pulse-steady-state equivalence and common rate scaling are treated as auxiliary linear-system facts. The central result is a structural non-identifiability theorem: if a reactive exit qj and a dark-loss exit lj from state j are not independently observed, then any redistribution q′ j + l′j = qj + lj leaves K, all non-reactive optical observables, and all spectral signals unchanged, while the reaction yield changes by ∆ΦR = δ (Ru)j . A one-state counterexample and a Jacobian analysis of the two-state thermally activated delayed fluorescence model with eight independent parameters θ = (kF , kP , kS,nr, kT,nr, i, r, qS, qT ) show that the luminescence observation map including fluorescence and phosphorescence, Y = (kF , kS, kT , ir, kP i), has rank 5 and a three-dimensional null space. Two directions reallocate reactive and dark-loss exits on the singlet and triplet states while leaving all luminescence observables unchanged; the third reallocates internal coupling and phosphorescence, and changes ΦR if and only if the triplet reaction exit qT is nonzero. A conditional experimental design table shows how direct product detection, state-selective observations, and multi-condition quenching restore identifiability. The results clarify when lifetime, delayed fluorescence, and transient absorption can be used to infer reaction quantum yields, and when they cannot.",
  "abstract_shown": true,
  "affiliations": [
    "Technical Institute of Physics and Chemistry",
    "Chinese Academy of Sciences"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 1,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Chen Ye",
      "orcid": "0000-0003-2952-6586"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/e2bm0gr6r6ytj.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010306/v1",
  "fulltext_url": null,
  "id": "e2bm0gr6r6ytj",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010306/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1606|Photochemistry and Electron Transfer Studies"
    ]
  ],
  "openalex": "W7221616970",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010306/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-12",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/e2bm0gr6r6ytj.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15010306",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010306/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1606|Photochemistry and Electron Transfer Studies",
      "subfield": "physical"
    }
  ],
  "title": "Structural Non-Identifiability of Photochemical Reaction Yields from Linear Optical Observables",
  "title_text": "Structural Non-Identifiability of Photochemical Reaction Yields from Linear Optical Observables",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/e2bm0gr6r6ytj",
  "venue": "ChemRxiv",
  "versions": []
}