The quantum-electrodynamic non-adiabatic emission (QED-NAE) is a type of radiatively assisted vibronic de-excitation due to electromagnetic vacuum fluctuations on non-adiabatic processes. Building on our previous work [Tsai et al., J. Phys. Chem. Lett. 14, 5924 (2023)], we extend the theory of the QED-NAE rate from a single cavity photonic mode to infinite photonic modes and calculate the QED-NAE rates of 9-cyanoanthracene at the first-principles level. To avoid the confusion, the quantum electrodynamic internal conversion process is renamed as “QED-NAE” in our present work. According to our theory, we identify three key factors influencing the QED-NAE processes: light–matter coupling strength (mode volume), mass-weighted orientation factor, and photonic density of states. The mode volume is the primary factor causing rate differences between the two scenarios. In a single cavity with a small mode volume, strong light–matter coupling strength boosts QED-NAE rates. In contrast, in free space with infinite photonic modes, weak coupling strength significantly reduces these rates. From a single cavity photonic mode to infinite photonic modes, the mass-weighted orientation factor only causes an 8π/3-fold increase in the QED-NAE rate. In free space, the photonic density of state exhibits a flat and quadratic distribution, which slightly reduces the QED-NAE rate. Our study shows that cavities can significantly enhance non-adiabatic QED effects while providing a robust analysis demonstrating that QED vibronic effects can be safely ignored in free space.
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Non-adiabatic quantum electrodynamic effects on electron–nucleus–photon systems: Single photonic mode vs infinite photonic modes
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21 January 2025
Research Article|
January 15 2025
Non-adiabatic quantum electrodynamic effects on electron–nucleus–photon systems: Single photonic mode vs infinite photonic modes
Special Collection:
2024 JCP Emerging Investigators Special Collection
Chih-En Shen
;
Chih-En Shen
(Formal analysis, Investigation, Methodology, Writing – original draft, Writing – review & editing)
1
Institute of Atomic and Molecular Sciences, Academia Sinica
, Taipei 10617, Taiwan
2
Department of Chemistry, National Taiwan University
, Taipei 10617, Taiwan
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Hung-Sheng Tsai
;
Hung-Sheng Tsai
(Formal analysis, Investigation, Methodology, Writing – original draft, Writing – review & editing)
1
Institute of Atomic and Molecular Sciences, Academia Sinica
, Taipei 10617, Taiwan
2
Department of Chemistry, National Taiwan University
, Taipei 10617, Taiwan
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Liang-Yan Hsu
Liang-Yan Hsu
a)
(Conceptualization, Formal analysis, Investigation, Methodology, Project administration, Supervision, Writing – original draft, Writing – review & editing)
1
Institute of Atomic and Molecular Sciences, Academia Sinica
, Taipei 10617, Taiwan
2
Department of Chemistry, National Taiwan University
, Taipei 10617, Taiwan
3
Physics Division, National Center for Theoretical Sciences
, Taipei 10617, Taiwan
a)Author to whom correspondence should be addressed: [email protected]
Search for other works by this author on:
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 162, 034107 (2025)
Article history
Received:
September 13 2024
Accepted:
November 08 2024
Citation
Chih-En Shen, Hung-Sheng Tsai, Liang-Yan Hsu; Non-adiabatic quantum electrodynamic effects on electron–nucleus–photon systems: Single photonic mode vs infinite photonic modes. J. Chem. Phys. 21 January 2025; 162 (3): 034107. https://doi.org/10.1063/5.0238657
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