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For molecules with negligible spin\u2013orbit coupling, the approach accounts for both radiative and non-radiative processes in complex photonic environments. Our theory reveals that the IC, fluorescence, and two quantum electrodynamic non-adiabatic emission (QED-NAE) channels can all be regarded as non-adiabatic processes. First-principles simulations not only recover the established Chance\u2013Prock\u2013Silbey description of emitter\u2013surface interactions but also quantify the contribution of vibrational overlap. We further find that cavity loss governs the competition between fluorescence and QED-NAE: reducing fluorescence in low-loss cavities results in the prominence of QED-NAE. By integrating radiative and non-radiative processes within a single macroscopic QED framework, this work provides a general foundation for photonic non-adiabatic phenomena and opens avenues for investigating electron\u2013nucleus\u2013photon and electron\u2013nucleus\u2013polariton interactions in photochemistry.<\/jats:p>","DOI":"10.1063\/5.0299368","type":"journal-article","created":{"date-parts":[[2025,11,6]],"date-time":"2025-11-06T11:20:46Z","timestamp":1762428046000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Unified theory of internal conversion and fluorescence under macroscopic quantum electrodynamics framework"],"prefix":"10.1063","volume":"163","author":[{"ORCID":"https:\/\/orcid.org\/0009-0006-4338-8094","authenticated-orcid":false,"given":"Chih-En","family":"Shen","sequence":"first","affiliation":[{"name":"Department of Chemistry, National Taiwan University 1 , Taipei 10617,","place":["Taiwan"]},{"name":"Institute of Atomic and Molecular Sciences, Academia Sinica 2 , Taipei 10617,","place":["Taiwan"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-3182-704X","authenticated-orcid":false,"given":"Hung-Sheng","family":"Tsai","sequence":"additional","affiliation":[{"name":"Department of Chemistry, National Taiwan University 1 , Taipei 10617,","place":["Taiwan"]},{"name":"Institute of Atomic and Molecular Sciences, Academia Sinica 2 , Taipei 10617,","place":["Taiwan"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9165-1033","authenticated-orcid":false,"given":"Liang-Yan","family":"Hsu","sequence":"additional","affiliation":[{"name":"Department of Chemistry, National Taiwan University 1 , Taipei 10617,","place":["Taiwan"]},{"name":"Institute of Atomic and Molecular Sciences, Academia Sinica 2 , Taipei 10617,","place":["Taiwan"]},{"name":"Physics Division, National Center for Theoretical Sciences 3 , Taipei 10617,","place":["Taiwan"]}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2025,11,6]]},"reference":[{"key":"2025110606204185400_c1","doi-asserted-by":"publisher","first-page":"58","DOI":"10.1002\/anie.200702506","volume":"47","year":"2008","journal-title":"Angew. 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